EP0591397A4 - Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol - Google Patents

Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol

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Publication number
EP0591397A4
EP0591397A4 EP92914366A EP92914366A EP0591397A4 EP 0591397 A4 EP0591397 A4 EP 0591397A4 EP 92914366 A EP92914366 A EP 92914366A EP 92914366 A EP92914366 A EP 92914366A EP 0591397 A4 EP0591397 A4 EP 0591397A4
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EP
European Patent Office
Prior art keywords
alkyl
laundry detergent
weight
surfactants
composition according
Prior art date
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Granted
Application number
EP92914366A
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EP0591397A1 (en
EP0591397B1 (en
Inventor
Gerard Marcel Baillely
Suzanne Powell
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • 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
    • C11D1/66—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
    • 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
    • C11D1/29—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
    • C11D1/52—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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This Application relates to fabric cleaning compositions and more particularly to fabric cleaning compositions capable of providing grease and oily stain removal.
  • the surfactant systems of commercially available fabric cleaning compositions are designed to remove a variety of soil types from the fabric surface.
  • the majority of such systems are based on one or more anionic surfactants with minor levels of other surfactant types such as nonionics, ampholytics and cationics.
  • a combination of a major proportion of anionic and a minor proportion of nonionic surfactant is commonly used to obtain an acceptable balance of particulate soil removal and grease and oily soil removal characteristics.
  • Detergent compositions incorporating surfactant systems in which the major component is nonionic are known in the art, e.g. EP-A-0006268 and GB 2206601 but any commercial application has tended to be of a specialist nature.
  • compositions based on anionic surfactants provide acceptable detergency over a broader spectrum of soil types, display greater compatibility with adjuncts such as optical brighteners and fabric softening additives and are also less aggressive towards fabric dyestuffs and washing machine components.
  • the present invention provides laundry detergent compositions which contain nonionic surfactant systems which comprise one or more polyhydroxy fatty acid amides and one or more additional nonionic surfactants. When included in such laundry detergent compositions, these nonionic surfactant systems unexpectedly improve the effectiveness of such compositions against greasy/oily stains across a broad range of laundry conditions.
  • nonionic surfactant systems comprising combinations of certain polyhydroxy fatty acid amides and one or more additional nonionic surfactants.
  • the polyhydroxy fatty acid amides have the formula
  • Ri is H, a C1-C4 hydrocarbyl, 2-hydroxyethyI, 2- hydroxypropyl or mixtures thereof, R ⁇ is a C5-C31 hydrocarbyl and
  • Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof.
  • the weight ratio of the polyhydroxy fatty acid amide to the additional nonionic surfactant can lie in the range from about 1:5 to about 5:1.
  • Other surfactant types such as anionic, cationic, ampholytic, zwitterionic and semipolar can be included as optional components and detergent compositions incorporating the surfactant systems are also disclosed.
  • detergent compositions incorporating nonionic surfactant systems of this general type comprising certain combinations of polyhydroxy fatty acid amides and water insoluble ethoxylated nonionic surfactants together with other water soluble surfactants provide unexpected oil and greasy soil removal benefits with no decrease in the detergency performance on other soil types.
  • N-alkyl pol hydroxyamide 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-alkanam1de Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K. HHdreth.
  • 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 add having 10-14 carbon atoms.
  • These compositions nay also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It 1s 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 add.
  • 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
  • Hildreth relates to amphiphilic 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 llposomes.
  • Included in this disclosure are compounds of the formula 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" 1s the residue of an aldose.
  • Kelkenberg, et al. relates to the use of N-polyhydroxy alkyl fatty add amides as thickening agents in aqueous detergent systems. Included are amides of the formula R ⁇ C(0)N(X)R2 wherein
  • Rl is a C ⁇ -Ci7 (preferably-C7-C17) alkyl, R 1s hydrogen, a CI-CJS
  • X is a polyhydroxy alkyl having four to seven carbon atoms, e.g.,
  • N-methyl, coconut fatty add glucamide N-methyl, coconut fatty add glucamide.
  • 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 sulfonat ⁇ s, oltfin sulfonate, sulfosuccinlc add half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty add polyglycol ester, polypropylene oxl t-polyethylent oxide mixed polymers, etc.
  • N-methyl coconut fatty add g1uc.j_.de/nonIon1c surfactant shampoo formulations are exemplified.
  • the N-polyhydroxy alkyl fatty add amides are said to have superior skin tolerance attributes.
  • U.S. Patent 2,982,737 issued May 2, 1961, to Boettner, e al., relates to detergent bars containing urea, sodium laury sulfate anionic surfactant, and an N-alkylglucamide nonioni surfactant which is selected from N-methyl,N-sorbityl lauramid and N-methyl, N-sorbityl myrlstamide.
  • glucamide surfactants are disclosed, for example, in D 2,226,872, published December 20, 1973, H. W. Eckert, et al. which relates to washing compositions comprising one or mor surfactants and builder salts selected from polymeric phosphates sequestering agents, and washing alkalis, Improved by the additio of an N-acylpolyhydroxyalkyl-amine of the formul RlC(0)N(R2)CH2(CH0H) n CH20H, wherein Ri is a C1-C3 alkyl, R 2 is C10-C22 alkyl, and n 1s 3 or 4.
  • the N-acylpolyhydroxyalkyl-amin Is added as a soil suspending agent.
  • Patent 3,654,166, Issued April 4, 1972, to H. W. Eckert, et al. relates to detergent compositions comprising at least on surfactant selected from the group of anionic, zwitterlonlc, an nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxylalkyl compound of the formula R ⁇ N(Z)C(0)R wherein Ri 1s a C10-C22 alkyl, R2 1s a C7-C21 alkyl, Ri and R total from 23 to 39 carbon atoms, and Z 1s a polyhydroxyalkyl which can be -CH2(CHOH) m CH2 ⁇ H where 1s 3 or 4.
  • U.S. Patent 4,021,539, Issued May 3, 1977, to H. M ⁇ ller, e al. relates to skin treating cosmetic compositions containin N-polyhydroxylalkyl-amines which Include compounds of the formul RlN(R)CH(CHOH) ⁇ R2 wherein Ri 1s H, lower alkyl, hydroxy-lowe alkyl, or aminoalkyl, as well as heterocycllc a lnoalkyl, R 1s th SUM as Ri but both cannot be H, and R21s CH OH or C0OH.
  • N-polyhydroxylalkyl-amines which Include compounds of the formul RlN(R)CH(CHOH) ⁇ R2 wherein Ri 1s H, lower alkyl, hydroxy-lowe alkyl, or aminoalkyl, as well as heterocycllc a lnoalkyl, R 1s th SUM as Ri but both cannot be H, and R21s CH OH or C0OH.
  • French Patent 1,360,018, April 26, 1963, assigned t Commercial Solvents Corporation relates to solutions o formaldehyde stabilized against polymerization with the additio of amides of the formula RC(0)N(R ⁇ )G wherein R 1s a carboxyli add functionality having at least seven carbon atoms, Ri i hydrogen or a lower alkyl group, and G 1s a glydtol radical wit at least 5 carbon atoms.
  • Heins relate to glucamine derivatives useful as wetting and dispersing agent of the formula N(R)(R ⁇ )(R2) wherein R is a sugar residue o glucamine, Ri is a C10-C20 alkyl radical, and R2 is a C1-C5 acy radical.
  • Patent 3,312,627 Issued April 4, 1967 to D. T. Hooker, discloses solid toilet bars that are substantially free of anioni detergents and alkaline builder materials, and which contai lithium soap of certain fatty adds, a nonionic surfactan selected from certain propylene oxide-ethylenedlamine-ethylen oxide condensates, propylene oxide-prop ene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can Include polyhydroxyamide o the formula RC(0)NRl(R2) wherein RC(0) contains from about 10 to about 14 carbon atoms, and R 1 and R 2 each are H or Cj-Ce alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substltuent hydroxyl groups of from 2 to about 6.
  • a nonionic lathering component which can Include polyhydroxyamide o the formula RC(0)NRl
  • nonionic surfactants in detergent compositions
  • GB Patent 1241754 which teaches that ethylene oxide adducts of C8-C 5 substantially unbranched monohydric alcohols having an average ethylene oxide content of from 10% to 51 % by weight can serve as detergency improvers for water soluble organic anionic or nonionic surfactants.
  • the improvers are used in a weight ratio of surfactant to improver of from 5:1 to 1:1.
  • the reference does not contemplate the combinations of the present invention that employ water insoluble polyhydroxy fatty acid amide surfactants as well as defined water insoluble ethyoxylated nonionic surfactants.
  • a laundry detergent composition useful for cleaning fabrics in automatic washing machines, said composition comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof, and optionally detergent builder compounds, said composition being characterised in that it comprises, in combination, (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having the formula
  • R is H, C -C4 hydrocarbyl, 2-hydroxyethyl, 2- hydroxypropyl or a mixture thereof
  • R2 is C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxy groups directly connected to said chain, or an alkyoxylated derivative thereof;
  • the composition is granular and comprises from 3 % to 15% by weight of anionic surfactant, from 1 % to 10% of component (a) and from 1% to 10% of component (b), the weight ratio of anionic surfactant to the combined weights of components (a) and (b) lying in the range from 1:3 to 3:1.
  • the anionic surfactant comprises a mixture of a major proportion of a water soluble C14-C15 alkyl sulfate and a minor proportion of a C12-C15 alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.
  • the detergent composition of the present invention comprise three essential components, viz. a polyhydroxy fatty acid amide, a water insoluble ethylene oxide adduct of a C11-C15 aliphatic alcohol and a water soluble surfactant that may be anionic, cationic, ampholytic or zwitterionic.
  • the polyhydroxy fatty add amide surfactant component of th present invention comprises compounds of the structural formula:
  • R 1 1s H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R* 1s a C5-C31 hydrocarbyl, preferably straight chain
  • Z 1s a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylattd derivativ (preferably ethoxylated or propoxylat ⁇ d) thereof.
  • Z preferabl will be derived from a reducing sugar 1n a reductive amination reaction; more preferably Z 1s a glydtyl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose com 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 1s by no means Intended to exclude othe suitable aw materials.
  • Z preferably will be selected from th group) consisting of -CH 2 -(CHOH) n -CH 2 ⁇ H, -CH(CH 2 ⁇ H)-(CHOH)n. ⁇ -CH 2 ⁇ H, -CH 2 -(CHOH)2(CHO « , )(CHOH)-CH 2 OH, wher n Is an Integer from 3 to 5, Inclusive, and ' 1s H or a cyclic o aliphatic monosacchaHd ⁇ , and alkoxylated derivatives thereof. Most preferred are glydtyls wherein n Is 4, particularl -CH2-(CHOH)4-CH2 ⁇ H.
  • R 1 cam be, for example, N-methyl, N-ethyl, M-propyl, M-lsopropyl, N-buty , N-2-hydroxy ethyl, or N-2-hydro ⁇ y propyl.
  • R 2 -C0-N ⁇ can be, for example, cocamide, stearamide, 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.
  • the most preferred polyhydroxy fatty acid amide has the general formula
  • polyhydroxy fatty add 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 condensat1on/am1dat1on step to form the N-alkyl, N-polyhydroxy fatty add amide product. Processes for making compositions containing polyhydroxy fatty add amides are disclosed, for example, 1n G.B.
  • Patent Specification 809,060 published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, Issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony H. Schwartz, Issued March 8, 1955, and U.S. Patent 1,985,424, Issued December 25, 1934 to Piggott, each of which 1s Incorporated herein by reference.
  • the amount of catalyst 1s 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 Q molar basis.
  • the reaction 1s preferably carried out at from about 138*C to about 170*C for typically from about 20 to about 90 minutes.
  • reaction 1s When trlglycerldes are utilized 1n the reaction mixture as the fatty ester source, the reaction 1s also preferably carried out using from about 1 to about 10 weight % of a phase transfer 5 agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosldes, linear glycamlde surfactant, and mixtures thereof.
  • a phase transfer 5 agent calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosldes, linear glycamlde surfactant, and mixtures thereof.
  • this process 1s carried out as follows: 0 (a) preheating the fatty ester to about 138 * C to about 170 * C; (b) adding the N-alkyl or N-hydroxyal yl glucamine to the heated fatty add ester and mixing to the extent needed to form a two-phase 11quid/11quid mixture; 5 (c) mixing the catalyst Into the reaction mixture; and (d) stirring for the specified reaction time.
  • the polyhydroxy "fatty add* amide materials used herein also 5 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.
  • polyhydroxy fatty acid amide materials are sourced from tallow fat such that R.2 is a C15-C17 straight chain alkyl group.
  • 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 compositions 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.
  • the polyhydroxy fatty acid amide component is present at a level of at least 1% by weight of the composition, more preferably at a level of from 1% to 10% by weight and most preferably at a level of from 2% to 6% by weight.
  • Laundry detergent compositions of the present invention comprise, in addition to the polyhydroxy fatty acid amide component, one or more of the nonionic surfactants described herein.
  • the nonionic surfactants described herein will hereinafter by referred to as "additional nonionic surfactants.”
  • additional nonionic surfactants Nonionic compounds other than these additional nonionic surfactants may be optionally included in the nonionic surfactant system of the present invention.
  • These other, optional nonionic compounds will hereinafter be referred to as “optional nonionics.” Without intending to be limited thereby, it is believed that when such optional nonionics are included in the nonionic surfactant system of the present invention, they do not provide the unexpected stain-removal benefits already described herein.
  • Primary C11-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol comprise the additional nonionic surfactants useful in compositions of the present invention.
  • Such alcohol ethyoxylates should have an ethylene oxide content of less than 50% by weight and should be water insoluble.
  • a preferred aliphatic alcohol ethoxylate is a linear or substantially linear aliphatic alcohol containing an average of 12-15 carbon atoms in the alkyl chain, ethoxylated with an average of three ethoxy groups per mole of alcohol.
  • the additional nonionic surfactant is present at a level of at least 1%, preferably from 1% to 10% and more preferably from 1% to 6% by weight of the composition.
  • the third essential component of laundry detergent compositions in accordance with the invention is one or more water soluble surfactants selected from anionic, cationic, ampholytic and zwitterionic surfactants.
  • the laundry detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present invention, one or more anionic surfactants as described below.
  • Alkyl ester sulfonate surfactants hereof include linear esters of C8- 20 carboxylic adds (I.e., fatty adds) 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 oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
  • R3 1S a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R* is a C_-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
  • Suitable salt-forming cations include metals such as sodium, potassium, and llthrum, and substituted or unsubstltuted ammonium cations, such as monoethanolamine, d1ethanolamine, and tr1ethanolamine.
  • R3 is C_Q-Ci6 alkyl, and R* 1s methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R31S Cio-Ci ⁇ alkyl. Alkvl Sulfate Surfactant
  • Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M 1s H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trim ⁇ thyl ammonium) cations and quaternary a ⁇ rnonium cations such as tetramethyl -ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from al kyl amines such as ethyl amine, di ethyl amine, tri ethyl amine, and mixture
  • Alkyl chains of 12-16 carbon atoms, more preferably 14-15 carbon atoms are preferred.
  • Al kyl alkoxylated sul fate surfactants hereof are water sol uble salts or adds of the formula R0(A) m S03M wherein R is an unsubstltuted C10-C24 al kyl or hydroxyal kyl group having a C10-C24 al kyl component, preferably a C12-C20 alkyl or hydroxyalkyl , more preferably an alkyl group having from 12 to 18 carbon atoms, especially from 12 to 15 carbon atoms.
  • A is an ethoxy or propoxy unit, ra 1s 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-ammonium cation.
  • a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • substituted ammonium cations include methyl-, dimethyl-, tr1methyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, d1ethylamine, tr1ethylamine, mixtures thereof, and the like.
  • Preferredexamples ofalkylalkoxylatedsulfatesurfactants are the C12- 18 alkyl ethoxy sulfates containinganaverage ofup to three ethoxygroupspermole ofalkyl ethoxy sulfate.
  • a particularly preferred surfactant is Ci2-Cl5 a ⁇ Y*i polyethoxylate (3.0) sulfate (C12- 5 E(3.0)M).
  • Other exemplary surfactants include C12- 8 alkyl polyethoxylate (1.0) sulfate (C12-C18 E(l.O)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-Ci8E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (Ci2-C ⁇ E(3.0)M), and C12-C18 alkyl polyethoxyl te (4.0) sulfate (Ci2-Ci8E(4.0)M), wherein M is conveniently selected fross sodium and potassium.
  • ⁇ ther Anionic Surfactants include C12- 8 alkyl polyethoxylate (1.0) sulfate (C12-C18 E(l.O)
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (Including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, d1- and tr1ethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, C8-C24 oleflnsulfonates, sulfonated polycarboxy ⁇ c adds prepared by sulfona ion of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersvlfates (containing up to. 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol su fonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, 1seth1onates such as the acyl 1seth1onates, N-acyl taurates, alkyl sucdnamates and sulfosucdnates, monoesters of sulfosucdnates (especially saturated and unsaturated C12-C18 monoesters) and dlesters of sulfosucdnates (especially saturated and unsaturated C5-C12 dlesters), acyl sarcoslnates, sulfates of alkylpolylene glycol glycol glycol glyco
  • Resin adds and hydrogenated resin adds are also suitable, such as rosin, hydrogenated rosin, and resin adds and hydrogenated resin adds present 1n or derived from tall oil. Further examples are described 1n "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 Laugh!in, et al. at Column 23, l ine 58 through Column 29, l ine 23 (herein Incorporated by reference).
  • Preferred anionic surfactant systems employed in the laundry detergent compositions of the invention are free of alkyl benzene sulfonate salts.
  • a highly preferred system comprises a mixture of a major proportion of a water-soluble C14-C15 alkyl sulfate and a minor proportion of a C12- 5 alkyl ethoxysulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.
  • the laundry detergent compositions of the present invention typically comprise from about 1 % to about 20% , preferably from about 3 % to about 15% and most preferably from 5% to 10% by weight of anionic surfactants.
  • the laundry detergent compositions of the present Invention may also contain cationic, ampholytlc, zwUterionlc, and seal -polar surfactants
  • Cationic detersive surfactants suitable for use 1n the laundry detergent compositions of the present Invention are those having on* long-chain hydrocarbyl group.
  • Examples of such cationic surfactants include the amwmlusi surfactants such as alkyl dimethyl ammonium halog ⁇ nld ⁇ s, and those surfactants having the formula:
  • R& I an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoas In the alkyl chain, each R3 1S selected from, the group consisting of -CHsCI-t ⁇ -, -CH2CH(CH3)-, •CH2CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof; each R* Is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy ⁇ alkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2CH0H-CH0HCOR ⁇ CHOHCH2 ⁇ H wherein R* Is any hexose or hexose polymer having a molecular weight less: than about 1000, and hydrogen when y 1s not 0; R 5 .
  • the laundry detergent compositions of the present invention typically comprise from 0% to about 25%, preferably from about 3% to about 15% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocycllc secondary and tertiary amines in which the- aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substltuents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubi11zing group, e.g., carboxy, sulfonate, sulfate. See U.S.
  • laundry detergent compositions of the present Invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • Zw1tter1o ⁇ 1c surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocycllc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonlum or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to LaughUn 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.
  • the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such zwittarionic surfactants.
  • 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
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R3(0R4) 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* 1s an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x 1s from 0 to about 3; and each R5 1S 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 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 1n particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl d1hydroxy ethyl amine oxides.
  • the laundry detergent compositions of the present Invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the laundry detergent compositions of the present Invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the laundry detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.
  • the level of builder can vary widely depending upon the end use of the composition and Its desired physical form.
  • Liquid formulations typically comprise at least about 1%, more typically froa 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%, preferably froa about 15% to about 50% by weight of the detergent builder.
  • Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolamaonlua salts of poly- phosphates (exemplified by the trlpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phy ic add, silicates, carbonates (Including blcarbonates and sesqul- carbonates), sulfates, and alualnoslHcates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions canalsobeusedbutarenotpreferredatwashconditionslessthan about50°C, especiallylessthanabout40°C.
  • Preferredbuilder systems arealsofreeofpho ⁇ phatee.
  • silicate builders are the alkali metal silicates, particularly those having a ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodlua silicates.
  • layered silicates such as the layered sodlua silicates.
  • Preferred crystalline layered sodium silicates have the general formula
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A- 3742043, incorporated herein by reference.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ - -» ⁇ - Y - and - forms of Na2Si2 ⁇ 5.
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is ⁇ - a2Si2 ⁇ 5, NaSKS-6.
  • 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 sesqui-
  • Aluminosilicate builders are especially useful in the prese invention. Aluminosilicate builders are of great importance most currently marketed heavy duty granular deterge compositions, and can also be a significant builder ingredient i liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • Preferred * *alurainos11lcates are zeolite builders whic have the formula:
  • aluminosilicate 1on exchange materials ar commercially available. These alumlnoslHcates can be crystallin or amorphous in structure and can be naturally-occurring alumino silicates or synthetically derived. A method for producin aluminosilicate ion exchange materials 1s disclosed in U.S. Paten 3,985,669, Krumael, et al., Issued October 12, 1976, incorporate herein by reference. Preferred synthetic crystalline alumino silicate ion exchange materials useful herein are available unde the designations Zeolite A, Zeolite P (B), and Zeolite X. In a especially preferred embodiment, the crystalline aluminosilicat ion exchange material has the formu 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,l-d1phosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic add 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 benzylmethylIdene and halo methylidene phosphonates.
  • Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos.
  • Polycarboxylate builder can generally be added to the composition in add 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.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One Important category of poly- carboxylat ⁇ builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • Examples of useful ether polycarboxylates include oxydlsucdnate, as disclosed in Berg, U.S. Patent 3,128,287, Issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, Issued January 18, 1972, both of which are Incorporated herein by reference.
  • a specific type of ether polycarboxyl tes useful as builders in the present invention also include those having the general formula:
  • A is H or OH; B is H or -0-CH(C00X)-CH2(C00X); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate dlsuccinlc 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.
  • ether hydroxypolycarboxylates represented by the structure:
  • Still other ether polycarboxylates include copolymers of ⁇ aleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-tr_1hydroxy benzene-2, 4, 6-tr1sulfonic add, and carboxymethyl- oxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of poly- acetic acids. Examples of 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, succinlc add, polymalelc add, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxyllc add, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citric builders e.g., dtric 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 laundry detergent compositions of the present invention are the 3,3-d1carboxy-4-oxa-l,6-hexaned1oates and the related compounds disclosed 1n U.S. Patent 4,566,984, Bush, issued January 28, 1986, Incorporated herein by reference.
  • Useful succinic acid builders include the C5-C20 alkyl succinlc acids and salts thereof. A particularly preferred compound of this type Is dodecenylsucdnlc add.
  • Alkyl succinlc adds typically are of the general formula R-CH(COOH)CH2(COOH) I.e., derivatives of succinic add, wherein R 1s hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described 1n the above-mentioned patents.
  • R 1s hydrocarbon e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described 1n the above-mentioned patents.
  • sucdnate builders are preferably used in the form of their water-soluble salts, Including the sodium, potassium, ammonium and alkanolammonium salts.
  • Specific examples of sucdnate builders include: lauryl- sucdnate, myristylsucdnate, palaltylsuc nate, 2-dodecenyl- sucdnate (preferred), 2-pentadecenylsucdnate, and the like.
  • Laurylsuccinates 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, carboxymethyloxysuccinate, cis-cyclo- hexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dlspersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polyacetal carboxy- lates are the polyacetal carboxy- lates 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 polymerization conditions, an ester of glyoxylic add 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 1n 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 homo- and copolymers of aliphatic carboxylic adds such as maleic add, itaeon1c add, mesaconlc add, fu arlc add, aeonitic add, dtraconlc add.and methylenemalon1c add.
  • hydrocarbyls can be utilized.
  • monocarboxyllc adds, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C10-C 0 are typically utilized.
  • the hydrocarbyls can be saturated or unsaturated.
  • ____L_L_L_L_L_L_L_L_L_i Detersive enzymes can be Included In the laundry detergent compositions of the present invention 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, Upases, 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 subtil1s1ns which are obtained from particular strains of B.subtil1s and B.licheniforms. Another suitable protease 1s 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 1n British patent specification No. 1,243,784 of Novo.
  • proteases 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 B1o-Synthet1cs, Inc. (The Netherlands).
  • proteolytic enzymes especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B.
  • Protease A and methods for Its preparation are described 1n European Patent Application 130,756, published January 9, 1985, Incorporated herein by reference.
  • Protease B 1s a proteolytic enzyme which differs from Protease A in that 1t has a leudne substituted for tyrosine in position 217 1n Its amino add sequence.
  • Protease B Is described in European Patent Application Serial No. 87303761.8f 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.
  • Amylolytlc 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. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, Incorporated herein by reference, which discloses fungal cellulase produced from Hum1cola insol ⁇ ns. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2.247.832. Examples of such cellulases are cellulases produced by a strain of Humlcola Insolens (Huaicola grlsea var.
  • thermoidea particularly the Humlcola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeroaonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolab ⁇ lla Auricula Sol nder).
  • Suitable Upas ⁇ enzymes for detergent usage include those produced by microorganisms of the Pseudoaonas group, such as Pseudoaonas stutzerl ATCC 19.154, as disclosed 1n British Patent No. 1,372,034, Incorporated herein by reference.
  • Suitable Upases include those which show, a positive laaunologlcal cross-reaction with the antibody of the llpase, produced by the microorganism Pswdomo ⁇ is fluortsctns IAM 1057. This llpase and a method for Its purification have been described 1n Japanese Patent Application No. 53-20487, laid open to public Inspection on February 24, 1978. This llpase Is available froa Aaano Pharmaceutical Co.
  • Aaano-P Such Upases of the present Invention should show a positive laaunologlcal cross reaction with the Aaano-P antibody, using the standard and well-known 1maunod1ffusion procedure according to Ouchtsriony (Acta. Med. Scan., 133, pages 76-79 (1950)). These Upases, and a method for their 1mmuno1og1cal cross-reaction wi Amano-P, are also described in U.S. Patent 4,707,291, Thorn et al.
  • Typical examples thereof are the Amano-P Upase, the lipase PseudonoMS frigl PERM P 1339 (available under the trade na .Amano-8), Upase ex Psu*doaon»s nitrortductns var. l ipolytic FERM P 1338 (available under the trade name Aaano-CES), Upases e C romobtcter viscosuM, e.g. Chromobtcfr viseosua var.
  • Peroxidas ⁇ enzymes are used 1n 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.
  • Peroxidas ⁇ enzymes are known 1n the art, and Include, for example, horseradish p ⁇ roxidas ⁇ , Hgnlnase, and haloperoxldase such as chloro- and bromo-p ⁇ roxidas ⁇ .
  • Perox1dase-conta1n1ng detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by 0.
  • Enzya ⁇ s are normally Incorporated at levels sufficient to provide up to about 5 ag by weight, more typically about 0.05 mg to about 3 ag, of active enzyae per gra ⁇ of the composition.
  • the enzymes are preferably coated prilled with additives inert toward the enzymes to minimize du formation and improve storage stability. Techniques f accomplishing this are well known in the art. In liqu formulations, an enzyme stabilization system is preferab utilized. Enzyme stabilization techniques for aqueous deterge compositions are well known in the art.
  • o technique for enzyme stabilization in aqueous solutions involv the use of free calcium ions from sources such as calcium acetat calcium formate, and caldum propionate.
  • Calcium ions can be us in combination with short chain carboxylic add salts, preferabl formates. See, for example, U.S. Patent 4,318,818, Letton, al., issued March 9, 1982, incorporated herein by reference.
  • Non-boric aci and borate stabilizers are preferred. Enzyae stabilizatio systeas are also described, for example, in U.S. Patent 4,261,868, 3,600,319, and 3,519,570. Bleaching Compounds - Bleaching Aoents and Bleach Activators
  • the laundry detergent compositions of the present inventio may contain bleaching agents or bleaching compositions containin bleaching agent and one or more bleach activators.
  • present bleaching compounds will typically comprise from about 1 to about 20X, more typically froa about 1% to about 10%, of suc laundry detergent composition.
  • bleaching compounds are optional components in non-11quid formulations, e.g., granula detergents. If present, the amount of bleach activators will typical ly be from about 0.1% to about 60%, more typical ly fro about 0.5% to about 40% of the bl eaching composition .
  • the bleaching agents used herein can be any of the bleachin agents useful for detergent compositions 1n textil e cl eaning, har surface cleaning, or other cleaning purposes that are now known o become known.
  • bleaching agent that can be used encompasses percarboxyl lc add bleaching agents and salts thereof. Suitable examples of this class of agents include agneslua monoperoxy- phthalate h ⁇ xahydrat ⁇ , the eagneslua salt of aeta-chloro perbenzolc add, 4-nonylaa1no-4-oxop ⁇ roxybutyr1c add and diperoxydodecanedlolc ac d. Such bleaching agents are disclosed
  • the laundry detergent compositions of the present invention will generally include a peroxygen bleaching agent, usually an inorganic perhydrate bleach, normally in the form of the sodium salt.
  • a peroxygen bleaching agent usually an inorganic perhydrate bleach, normally in the form of the sodium salt.
  • Suitable perhydrate bleaches may be any of the inorganic salts such as. perborate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal normally sodium, perborate or percarbonate.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate
  • Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to
  • silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be included in the coating.
  • 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.
  • bleach activators include the tetraacetyi alkylene diamines, particularly tetraacetyl ethylene cLiamine (TAED) and tetraacetyl glycouril (TAGU).
  • TAED tetraacetyl ethylene cLiamine
  • TAGU tetraacetyl glycouril
  • 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 froa about 6 to about 10 carbon atoas and L is a leaving group, the conjugate acid of which has a pK « 1n the range of froa about 4 to about 13.
  • bleach activators are described 1n 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 1n the art and can be utilized herein.
  • Non- oxygen bleaching agent of particular Interest includes photo- activated bleaching agents such as the sulfonated zinc and/or alualnua phthalocyanin ⁇ s. These materials can be deposited upon the substrate during the washing process. Upon Irradiation with light, In the presence of oxygen, such as by hanging clothes out to dry 1n the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate Is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al., incorporated herein by reference.
  • detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • any polymeric soil release agents known to those skilled in the art can be employed in the laundry detergent compositions of the present invention.
  • Polymeric soil release agents are characterized by having both hydrophllic segments, to hydrophilize the surface of hydrophoblc fibers, such as polyester and nylon, and hydrophoblc 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 hydrophllic 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 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 Methocel** (Dow).
  • Cellulosic soil release agents also Include those selected froa the group consisting of C1-C4 alkyl and Ca hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcel ulose, and hydroxybutyl methylcellulose.
  • C1-C4 alkyl and Ca hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcel ulose, and hydroxybutyl methylcellulose.
  • a variety of cellulose derivatives useful as soil release polymers are disclosed 1n 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(vlnyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(v1nyl acetate) grafted onto polyal ylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vlnyl ester) e.g., Ci-C ⁇ vinyl esters
  • poly(v1nyl acetate) grafted onto polyal ylene oxide backbones such as polyethylene oxide backbones.
  • Such materials are known in the art and are describe d in European Patent Application 0219048, published April 22, 1987 by ud, et al.
  • Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTH HP-22, available from BASF (West Germany).
  • 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 55,000. See U.S. Patent 3,959,230 to
  • Another preferred polymeric soil release agent 1 s 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 Oupont) and H1lease R T (from ICI). These polymers and methods of their preparation are more fully described 1n U.S. Patent 4,702,857, Issued October 27, 1987 to Goss ⁇ link, which 1s Incorporated herein by reference.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomerlc ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from ally! alcohol ethoxylate, dimethylterephthalate, and 1,2 propylene diol, wherein 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 4968451, issued 6 November1990 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-polyoxy- ethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., the anionic end-capped ollgomeric 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 1s a C1-C4 alkyl, or preferably methyl, all of these patents being Incorporated herein by reference.
  • Additional soil release polymers include the soil release polymers of U.S. Patent 4,877,896, Issued October 31, 1989 to Haldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being Incorporated herein by reference.
  • the terephthalate esters contain unsymmetHcally substituted oxy-l,2-a1ky1eneoxy units.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, preferably from about 0.1% to about 5.0%,.more preferably froa about 0.2% to about 3.0% by weight of the laundry detergent compositions of the present Invention.
  • the laundry detergent compositions of the present invention may also optionally contain one or more Iron and manganese chelating agents as a builder adjunct material.
  • Such chelating agents can be selected froa the group consisting of amino carboxylates, amino phosphonates, polyfunctlonally-substHuted aromatic chelating agents and alxtures 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 ex ⁇ ceptional 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 - CH2 ⁇ N - (CH 2 ) X - COOM,
  • H is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, pref ⁇ erably 1.
  • these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Operable amine carboxylates include ethy1enediaminetetraacet tes, N-hydroxyethylethylenediaminetriacetates, nitri1otriacetates, ethylened1amine tetraproprionates, triethylenetetraaminehexa- acetates, diethylenetriaminepentaacetates, and ethanoldiglydnes, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
  • Amino phosphonates are also suitable for use as chelating agents in the laundry detergent compositions of the present Invention when at least low levels of total phosphorus are permitted 1n detergent compositions.
  • Compounds with one or more, preferably at least two, units of the substructure - CH2 ⁇ N - (CH 2 ) X - PO3M2, / wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x 1s from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakls (methylenephosphonates), nitrllotrls (methylenephosphonates) and dlethylenetriaminepentakis (methylenephosphonates).
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbo atoms.
  • Alkylene groups can be shared by substructures.
  • Polyfunctionally-substituted aromatic chelating agents ar also useful in the compositions herein. These materials ca comprise compounds having the general formula
  • R is -SO3H or -COOH or soluble salts thereo and mixtures thereof.
  • Alkaline detergent compositions can contain these materials in th form of alkali metal, ammonium or substituted ammonium (e.g. ono-or triethanol-amine) salts.
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions of the present Invention. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight o such compositions.
  • Clay soil removal/ant1-redepos1t1on agents useful in the laundry detergent compositions of the present Invention include polyethylene glycols and water-soluble ethoxylated amines having clay soil removal and antl-redeposltlon properties.
  • Polyethylene glycol compounds useful 1n the laundry detergent compositions of the present Invention typically have a molecular weight 1n the range of from about 400 to about 100,000, preferably froa about 1,000 to about 20,000, more preferably from about 2,000 to about 12,000, most preferably froa about 4,000 to about 8,000.
  • Such compounds are commercially available and are sold as Carbowax*, which is available from Union Carbide, located in Danbury, Conn.
  • the water-soluble ethoxylated amines are preferably selecte d from the group consisting of: (1) ethoxylated monoa ines having the formula:
  • X is a nonionic group, an anionic group or mixture thereof
  • R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites
  • R* is C1-C alkylene, hydroxyalkylene,.
  • L is a hydrophi ⁇ c chain which contains the polyoxyalkylene moiety -_(R 5 0)m(CH2CH2 ⁇ ) n ]-, wherein ⁇ is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH CH2 ⁇ ) n - comprises at least about 50% by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and n is at least about 12; for said dia ines, 1s from 0 to about 3, and n is at least about 6 when R is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R 1 is other than C2-C3 alkylene, hydroxyalkylene or alken
  • the most preferred soil release and ant1-redeposit1on agent is ethoxylated tetraethylenepentamine.
  • 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/ant1-redepos1t1on agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionlc 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.
  • the most preferred soil release and ant1-redepos1t1on agents are ethoxylated tetraethylenepentamine and the polyethylene glycols having a molecular weight 1n the range of from about 4,000 to about 8,000.
  • Granular detergent compositions which contain such compounds typically contain from about 0.01% to about 10.0% by weight of the clay removal agent; liquid detergent compositions typically contain from about 0.01% to about 5.0% by weight.
  • Polymeric polycarboxylate dispersing agents can advantageously be utilized in the laundry detergent compositions of the present invention. These materials can aid in calcium and magnesium hardness control. In addition to acting as a builder adjunct analogously to the polycarboxylate described above in the Builder description, it 1s believed, though it 1s not intended to be limited by theory, that these higher molecular weight dispersing agents can further enhance overall detergent builder performance by inhibiting crystal growth of inorganics, by particulate soil peptization, and by antiredepositions, when used in combination with other builders including lower molecular weight pol carboxyl tes.
  • polycarboxylate materials which can be employed as the polymeric polycarboxylate dispersing agent are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula X Z
  • X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxy- methyl; a salt-forming cation and n is from about 30 to about 400.
  • X is hydrogen or hydroxy
  • Z is hydrogen
  • M is hydrogen, alkali metal, ammonia or substituted ammonium.
  • Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolyerlzing suitable unsaturated monomers, preferably in their add form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric poly- carboxylates include acrylic add, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalon1c acid.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic add.
  • acrylic add-based polymers which are useful herein are the water-soluble salts of polymerized acrylic add.
  • the average molecular weight of such polymers in the add form ranges from about 2,000 to 10,000, more preferably froa about 4,000 to 7,000 and most preferably froa about 4,000 to 5,000.
  • Water-soluble salts of such acrylic add ho opoiymers include, for example, the alkali metal, amaonlua and substituted ammonium salts. Soluble polymers of this type are known materials.
  • Use of polyacrylates of this type 1n detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967. This patent 1s Incorporated herein by reference.
  • Acryllc/mal ⁇ ic-based copolymers may also be used as a preferred component of the dispersing agent.
  • Such materials include the water-soluble salts of copolymers of acrylic add and maleic acid.
  • the average molecular weight of such copolymers in the add form ranges froa about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably froa about 7,000 to 60,000.
  • the ratio of aerylate to aaleate segaents 1n such copolymers will generally range froa about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic add/ maleic add copolymers can include, for exaaple, the alkali metal, amaonlua and substituted aaeonlua 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 1s Incorporated herein by reference.
  • the polymeric dispersing agents will generally comprise from about 0.2% to about 10%, preferably from about 1% to about 5% by weight of the laundry detergent compositions.
  • Brightener Optical brighteners or other brightening or whitening agents known to those skilled in the art can be incorporated into the laundry detergent compositions of the present Invention. However, the choice of brightener 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 1s 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.
  • Commercial optical brighteners can be classified into subgroups which Include, but are not necessarily limited to, derivatives of stilbene, pyrazollne, couraarin, carboxylic acid, methlnecyanlnes, d1benzoth1phene-5,5-d1ox1de, azoles, 5- and 6-meabered-r1ng heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnlk, Published by John Wiley & Sons, New York (1982), the disclosure of which Is Incorporated herein by
  • Stilbene derivatives include, but are not necessarily limited to, derivatives of bis(tr1az1nyl)amino-stilbene; bisacylamino derivatives of stilbene; trlazol ⁇ derivatives of stilbene; oxadlazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
  • b1s(tr1az1nyl)am1nost1lbene may be prepared from 4,4'-d1amine-stilbene-2,2'-d1sulfonic acid.
  • Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-positio ⁇ , and in the 3- and 7-positions.
  • Carboxylic acid derivatives 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 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 Zahradnlk reference.
  • the styrylazoles can be further subclassified into styryl- benzoxazoles, styrylimldazoles and styrylth1azoles, as disclosed on page 78 of the Zahradnlk reference. It will be understood that these three Identified subclasses may not necessarily reflect an exhaustive 11st of subgroups into which styrylazoles may be subclassified.
  • Other optical brighteners are the derivatives of d1benzoth1ophene-5,5-d1ox1de disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology.
  • optical brighteners are azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcategorized Into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk-Othmer reference.
  • Still other optical brighteners are the derivatives of 6-membered-ring heterocycles disclosed 1n the Kirk-Othmer reference. Examples of such compounds Include brighteners derived from-pyrazlne and brighteners derived froa 4-am1nonaphthalamide. In addition to the brighteners already described, miscellaneous agents may also be useful as brighteners.
  • miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include l-hydroxy-3,6,8-pyrenetri- sulfonic acid; 2,4-dimethoxy-l,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolonedisulfonic acid; and derivatives of pyrazoline- quinoline.
  • optical brighteners 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
  • C1ba-Ge1gy available from C1ba-Ge1gy
  • Arctic White CC available from Hilton-Davis, located in Italy
  • 2-(4-styryl- phenyl)-2H-naphthol[l,2-d]triazoles 4,4'-b1s-(l,2,3-tr1azol-2- yl)-stilbenes
  • 4,4'-bis(styryl)bisphenyls 4,4'-bis(styryl)bisphenyls
  • the y-am1no- coumarins include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from C1ba-Ge1gy; Arctic White CC and Artie White CWD, available from Hilton-Davis, located in Italy
  • these brighteners include 4-methyl-7-diethylamino coumarln; l,2-b1s(-benz1midazol-2-yl)- ethylene; 1,3-diphenylphrazoHnes; 2,5-b1s(benzoxazol-2-yl)- thiophene; 2-styryl-naphth-[l,2-d]-oxazole; and 2-(stilbene-4-yl)- 2H-naphtho[l,2-d]triazole.
  • Still other optical brighteners include those disclosed in U.S. Patent 3,646,015, Issued February 29, 1972 to Hamilton, the disclosure of which is Incorporated herein by reference.
  • the optical brighteners will generally comprise from about 0.05% to about 2.0%, preferably from about 0.1% to about 1.0% by weight of the laundry detergent compositions. Suds Suppressors
  • Suds suppressors can be desirable because the polyhydroxy fatty add 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 polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic 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.
  • suds suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.
  • a wide variety of materials may be used as suds suppressors. 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 monocarboxy1ic 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 monocarboxyl1c fatty adds, 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 laundry detergent compositions of the present invention may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example, high molecular weight hydrocarbons such as paraffin, fatty add esters (e.g., fatty add trlglycerldes), fatty acid esters of monovalent alcohols, aliphatic 18-C 0 ketones (e.g. stearone), etc.
  • N-alkylated amino trlazlnes such as tr1- to hexa-alkylmelamines or di- to tetra-alkyld1amine chlortrlazlnes 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, preferably 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 heterocycllc 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 si11cone suds suppressors.
  • This category includes the use of polyorganoslloxane oils, such as polydi ethylsiloxane, dispersions or emulsions of polyorganoslloxane oils or resins, and combinations of polyorganoslloxane with silica particles wherein the polyorganoslloxane 1s chemlsorb ⁇ d of fused onto the silica.
  • SI11cone 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
  • 3,455,839 which relates to compositions and processes for defoaaing aqueous solutions by Incorporating therein small amounts of polydimethylsiloxane fluids.
  • siHcon ⁇ and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • SiHcone defoaaers 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; (11) from about 5 to about 50 parts per 100 parts by weight of
  • siloxane resin composed of (CH3)3 SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SIO1 2 units and to SIO2 units of from about 0.6:1 to about 1.2:1; and (111) from about 1 to about 20 parts per 100 parts by weight of
  • Suds suppressors when utilized, are present in a "suds suppressing amount.”
  • Suds suppressing amount is meant that the for ulator of the composition can select an amount of this suds controlling agent that will control the suds to the extent desired.
  • the amount of suds control will vary with the detergent surfactant selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent 1s used to achieve the desired suds control than with low foaming surfactants.
  • the laundry detergent compositions of the present invention will generally comprise froa 0% to about 5% of suds suppressor.
  • aonocarboxyllc fatty adds, and salts, thereof When utilized as suds suppressors, aonocarboxyllc fatty adds, and salts, thereof, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor 1s utilized. SiHcone 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 primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably froa about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.255. 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 generally utilized in amounts ranging from about 0.1% to about 2% by weight of the compositions.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • Other Ingredients are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • laundry detergent compositions of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and iso- prcpanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,3-propanedlol) can also be used.
  • the laundry detergent compositions of the present invention 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, alkali, adds, etc., and are well _known to those skilled 1n the art. _
  • 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 containing the nonionic surfactant system of the present invention, wherein the weight ratio of polyhydroxy fatty acid amide to additional surfactant in the nonionic surfactant system is in the range of from about 1:5 to about 5:1, in the presence of a solvent such as water or a water-mi proficient solvent (e.g., primary and secondary alcohols).
  • a solvent such as water or a water-mi proficient solvent (e.g., primary and secondary alcohols).
  • Agitation is preferably provided for enhancing cleaning.
  • Suitable means for providing agitation include rubbing by hand preferably with the aid of a brush, or other cleaning device, automatic laundry washing machines, automatic dishwashers, etc.
  • gXPERI ENAL This exemplifies a process for making a N-methyl, 1-deoxy- glucityl 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 1s Important in case of very rapid methanol evolution) to which 1s connected an efficient collecting condenser and vacuum outlet.
  • 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 1t 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, Aldrlch, 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 1s 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.
  • TAED Tetraacetyl ethylene diamine Silicate Amorphous Sodium Silicate (Si ⁇ 2:Na2 ⁇ ratio normally follows).
  • MA/AA Copolymer of 1:4 maleic anhydride/acrylic acid average molecular weight about 80,000.
  • AEG Lavamat 980 automatic washing machines were used to carry out a similar comparison of the products.
  • Six replicates for each product were carried out.
  • Each wash load comprised 3kg of realistically soiled ballast fabrics composed of cotton sheets and towels together with polycotton items to give a cotton:polycotton weight ratio of approximately 3:1, together with sets of stained swatches.
  • the stain sets comprised:
  • the LH column shows the advantage for Composition A over Composition B while the RH column shows the advantage for Composition A over Composition C.
  • composition A in accordance with the invention, provides stain removal benefits relative to Composition C over a wide spectrum of soil types and fabrics.
  • the comparison of compositions A&B shows the surprising benefit provided by the use of a combination in accordance with the invention relative to that provided by use of a higher level of the polyhydroxy fatty acid amide alone.
  • Composition A of Example I was compared to a commercially available detergent composition (D) which differed from Composition A only in that the 45AS, 25AE3S, TGA and 25E3 components were replaced by 7.6% C12 LAS, 3 % 45E7 and 1.1 % TAEn.
  • the comparison was carried out in AEG Lavamat 980 washing machines using the wash conditions and procedure of Example 1 and a variety of stains on cotton, polycotton and polyester fabric swatches. Assessment of the washed fabric swatches by an expert panel using a five point Scheffe * scale showed that
  • Composition A provided a stain removal benefit over Composition D of
  • Composition A of Example I was compared to that of two further detergent Compositions D and E which differed from A only in that the 25E3 component was replaced by 68E3 and 68E5 respectively, where 68E3 and 68E5 are Ci6-C ⁇ 8 predominantly linear primary alcohols condensed with an average of three and five moles of ethylene oxide respectively.
  • the performance comparisons were made using the conditions and procedure of the tergotometer test of Example I.
  • composition A in accordance with the invention, provided significant stain removal benefits over both compositions D and E, neither of which is a composition in accord with the invention.
  • the LH column shows the advantage for Composition A over Composition D while the RH column shows the advantage for Composition A over Composition E.

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Abstract

The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having formula (I), wherein R1 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 linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) at least 1 % by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 % by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

Description

LAUNDRY D_____RGENT CONTAINING A POLYHYDROXY FATTY AMIDE AND __-.-X-I.UBLE ETHOXYLATED ALCOHOL
This Application relates to fabric cleaning compositions and more particularly to fabric cleaning compositions capable of providing grease and oily stain removal.
The surfactant systems of commercially available fabric cleaning compositions are designed to remove a variety of soil types from the fabric surface. The majority of such systems are based on one or more anionic surfactants with minor levels of other surfactant types such as nonionics, ampholytics and cationics. In particular, a combination of a major proportion of anionic and a minor proportion of nonionic surfactant is commonly used to obtain an acceptable balance of particulate soil removal and grease and oily soil removal characteristics. Detergent compositions incorporating surfactant systems in which the major component is nonionic are known in the art, e.g. EP-A-0006268 and GB 2206601 but any commercial application has tended to be of a specialist nature. This is because compositions based on anionic surfactants provide acceptable detergency over a broader spectrum of soil types, display greater compatibility with adjuncts such as optical brighteners and fabric softening additives and are also less aggressive towards fabric dyestuffs and washing machine components.
Accordingly, a need still exists for detergent compositions displaying improved grease and oily soil removal without any sacrifice in the removal of other soil types and without impact on the performance of other detergent ingredients. The present invention provides laundry detergent compositions which contain nonionic surfactant systems which comprise one or more polyhydroxy fatty acid amides and one or more additional nonionic surfactants. When included in such laundry detergent compositions, these nonionic surfactant systems unexpectedly improve the effectiveness of such compositions against greasy/oily stains across a broad range of laundry conditions.
The commonly assigned copending US Application Serial No. 07/578760 tattorney's docket No. 4265) filed 28 September 1990 discloses nonionic surfactant systems comprising combinations of certain polyhydroxy fatty acid amides and one or more additional nonionic surfactants. The polyhydroxy fatty acid amides have the formula
wherein Ri is H, a C1-C4 hydrocarbyl, 2-hydroxyethyI, 2- hydroxypropyl or mixtures thereof, R^ is a C5-C31 hydrocarbyl and
Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof. The weight ratio of the polyhydroxy fatty acid amide to the additional nonionic surfactant can lie in the range from about 1:5 to about 5:1. Other surfactant types such as anionic, cationic, ampholytic, zwitterionic and semipolar can be included as optional components and detergent compositions incorporating the surfactant systems are also disclosed.
The Applicant has unexpectedly found that detergent compositions incorporating nonionic surfactant systems of this general type comprising certain combinations of polyhydroxy fatty acid amides and water insoluble ethoxylated nonionic surfactants together with other water soluble surfactants provide unexpected oil and greasy soil removal benefits with no decrease in the detergency performance on other soil types.
(*see page 57Δ for Equivalent Application) BACKGROUND ART A variety of polyhydroxy fatty acid amides have been described in the art. N-acyl, N-methyl gluca ides, for example, are disclosed by J. . Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Ther otropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphlphiles," Liquid Crystals, 1988, Volume 3, No. 11, pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R. Hilgenfeld 1n "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl pol hydroxyamide surfactants has 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-alkanam1de Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K. HHdreth.
The use of 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 add having 10-14 carbon atoms. These compositions nay also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It 1s 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 add. The product of this reaction is said to be useable in aqueous detergent compositions without further purification. It is also known to prepare a sul uric ester of acylated glucamine as disclosed in U.S. Patent 2,717,894, issued September 13, 1955, to A. M. Schwartz. PCT International Application WO 83/04412, published December
22, 1983, by •_. Hildreth, relates to amphiphilic 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 llposomes. Included in this disclosure are compounds of the formula 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" 1s the residue of an aldose.
European Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty add amides as thickening agents in aqueous detergent systems. Included are amides of the formula RιC(0)N(X)R2 wherein
Rl is a Cχ-Ci7 (preferably-C7-C17) alkyl, R 1s hydrogen, a CI-CJS
(preferably i-Cς) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g.,
N-methyl, coconut fatty add glucamide. 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 sulfonatβs, oltfin sulfonate, sulfosuccinlc add half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty add polyglycol ester, polypropylene oxl t-polyethylent oxide mixed polymers, etc. Paraffin sulfonate/
N-methyl coconut fatty add g1uc.j_.de/nonIon1c surfactant shampoo formulations are exemplified. In addition to thickening attributes, the N-polyhydroxy alkyl fatty add amides are said to have superior skin tolerance attributes. - _> -
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, e al., relates to detergent bars containing urea, sodium laury sulfate anionic surfactant, and an N-alkylglucamide nonioni surfactant which is selected from N-methyl,N-sorbityl lauramid and N-methyl, N-sorbityl myrlstamide.
Other glucamide surfactants are disclosed, for example, in D 2,226,872, published December 20, 1973, H. W. Eckert, et al. which relates to washing compositions comprising one or mor surfactants and builder salts selected from polymeric phosphates sequestering agents, and washing alkalis, Improved by the additio of an N-acylpolyhydroxyalkyl-amine of the formul RlC(0)N(R2)CH2(CH0H)nCH20H, wherein Ri is a C1-C3 alkyl, R2 is C10-C22 alkyl, and n 1s 3 or 4. The N-acylpolyhydroxyalkyl-amin Is added as a soil suspending agent. U.S. Patent 3,654,166, Issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least on surfactant selected from the group of anionic, zwitterlonlc, an nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxylalkyl compound of the formula RιN(Z)C(0)R wherein Ri 1s a C10-C22 alkyl, R2 1s a C7-C21 alkyl, Ri and R total from 23 to 39 carbon atoms, and Z 1s a polyhydroxyalkyl which can be -CH2(CHOH)mCH2θH where 1s 3 or 4.
U.S. Patent 4,021,539, Issued May 3, 1977, to H. Mδller, e al., relates to skin treating cosmetic compositions containin N-polyhydroxylalkyl-amines which Include compounds of the formul RlN(R)CH(CHOH)βR2 wherein Ri 1s H, lower alkyl, hydroxy-lowe alkyl, or aminoalkyl, as well as heterocycllc a lnoalkyl, R 1s th SUM as Ri but both cannot be H, and R21s CH OH or C0OH.
French Patent 1,360,018, April 26, 1963, assigned t Commercial Solvents Corporation, relates to solutions o formaldehyde stabilized against polymerization with the additio of amides of the formula RC(0)N(Rι)G wherein R 1s a carboxyli add functionality having at least seven carbon atoms, Ri i hydrogen or a lower alkyl group, and G 1s a glydtol radical wit at least 5 carbon atoms. German Patent 1,261,861, February 29, 1968, A. Heins, relate to glucamine derivatives useful as wetting and dispersing agent of the formula N(R)(Rι)(R2) wherein R is a sugar residue o glucamine, Ri is a C10-C20 alkyl radical, and R2 is a C1-C5 acy radical.
G.B. Patent 745,036, published February 15, 1956, assigned t Atlas Powder Company, relates to heterocycϋc amides an carboxylic esters thereof that are said to be useful as chemica intermediates, emulsifiers, wetting and dispersing agents detergents, textile softeners, etc. The compounds are expresse by the formula N(R)(Rι)C(0)R2 wherein R 1s the residue of a anhydrized hexane pentol or a carboxylic add ester thereof, i i a monovalent hydrocarbon radical, and -C(0)R2 1s the acyl radica of a carboxylic acid having from 2 to 25 carbon atoms. U.S. Patent 3,312,627, Issued April 4, 1967 to D. T. Hooker, discloses solid toilet bars that are substantially free of anioni detergents and alkaline builder materials, and which contai lithium soap of certain fatty adds, a nonionic surfactan selected from certain propylene oxide-ethylenedlamine-ethylen oxide condensates, propylene oxide-prop ene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can Include polyhydroxyamide o the formula RC(0)NRl(R2) wherein RC(0) contains from about 10 to about 14 carbon atoms, and R1 and R2 each are H or Cj-Ce alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substltuent hydroxyl groups of from 2 to about 6. A substantially similar disclosure Is found 1n U.S. Patent 3,312,626, also Issued April 4, 1967 to 0. T. Hooker. T e use of nonionic surfactants 1n detergent compositions is known 1n the art. U.S. Patent 3,654,166, Issued April 4, 1972 to Eckert et al., discloses detergent compositions comprising a surfactant selected from anlonlcs, zwltterlonlcs and nonlonlcs and an M-alkyl-N-acyl-N-polyhydroxyal yl compound. Another disclosure of the use of nonionic surfactants in detergent compositions is provided by GB Patent 1241754 which teaches that ethylene oxide adducts of C8-C 5 substantially unbranched monohydric alcohols having an average ethylene oxide content of from 10% to 51 % by weight can serve as detergency improvers for water soluble organic anionic or nonionic surfactants. The improvers are used in a weight ratio of surfactant to improver of from 5:1 to 1:1. However, the reference does not contemplate the combinations of the present invention that employ water insoluble polyhydroxy fatty acid amide surfactants as well as defined water insoluble ethyoxylated nonionic surfactants.
According to the present invention, there is provided a laundry detergent composition useful for cleaning fabrics in automatic washing machines, said composition comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof, and optionally detergent builder compounds, said composition being characterised in that it comprises, in combination, (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having the formula
where R is H, C -C4 hydrocarbyl, 2-hydroxyethyl, 2- hydroxypropyl or a mixture thereof, R2 is C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxy groups directly connected to said chain, or an alkyoxylated derivative thereof; and
(b) at least 1% by weight of the composition of a substantially water-insoluble ethoxylated C11-C 5 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50% by weight.
Preferably the composition is granular and comprises from 3 % to 15% by weight of anionic surfactant, from 1 % to 10% of component (a) and from 1% to 10% of component (b), the weight ratio of anionic surfactant to the combined weights of components (a) and (b) lying in the range from 1:3 to 3:1. More preferably the anionic surfactant comprises a mixture of a major proportion of a water soluble C14-C15 alkyl sulfate and a minor proportion of a C12-C15 alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.
The detergent composition of the present invention comprise three essential components, viz. a polyhydroxy fatty acid amide, a water insoluble ethylene oxide adduct of a C11-C15 aliphatic alcohol and a water soluble surfactant that may be anionic, cationic, ampholytic or zwitterionic.
- 9 -
Polvhvdroxy Fattv Acid Amide
The polyhydroxy fatty add amide surfactant component of th present invention comprises compounds of the structural formula:
0 Rl
If I
(I) RZ - C - N - Z wherein: R1 1s H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R* 1s a C5-C31 hydrocarbyl, preferably straight chain
C..-C19 alkyl or alkenyl, more preferably straight chain C|5-c alkyl or alkenyl, most preferably straight chain alkylor alkenyl, or mixture thereof; and Z 1s a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylattd derivativ (preferably ethoxylated or propoxylatβd) thereof. Z preferabl will be derived from a reducing sugar 1n a reductive amination reaction; more preferably Z 1s a glydtyl. Suitable reducing sugars Include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose com 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 1s by no means Intended to exclude othe suitable aw materials. Z preferably will be selected from th group) consisting of -CH2-(CHOH)n-CH2θH, -CH(CH2θH)-(CHOH)n.ι-CH2θH, -CH2-(CHOH)2(CHO«,)(CHOH)-CH2OH, wher n Is an Integer from 3 to 5, Inclusive, and ' 1s H or a cyclic o aliphatic monosacchaHdβ, and alkoxylated derivatives thereof. Most preferred are glydtyls wherein n Is 4, particularl -CH2-(CHOH)4-CH2θH.
-In Formula (I), R1 cam be, for example, N-methyl, N-ethyl, M-propyl, M-lsopropyl, N-buty , N-2-hydroxy ethyl, or N-2-hydroχy propyl. R2-C0-N< can be, for example, cocamide, stearamide, 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.
The most preferred polyhydroxy fatty acid amide has the general formula
0 CH3 Ii I
R2 - C - N - CH2 - (CHOH)4CH2θH wherein RZ 1S a cn-c]9 straight-chain alkyl or alkenyl group.
Methods for making polyhydroxy fatty add 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 condensat1on/am1dat1on step to form the N-alkyl, N-polyhydroxy fatty add amide product. Processes for making compositions containing polyhydroxy fatty add amides are disclosed, for example, 1n G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, Issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony H. Schwartz, Issued March 8, 1955, and U.S. Patent 1,985,424, Issued December 25, 1934 to Piggott, each of which 1s Incorporated herein by reference.
In a preferred process for producing N-alkyl or N-hydroxyalkyl, N-dtoxyglycityl fatty add amides wherein the glydtyl component 1s derived from glucose and the N-alkyl or N-hydroxyalkyl functionality 1s N-methyl* N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyal yl-glucamine with a fatty ester selected fro* fatty methyl esters, fatty ethyl esters, and fatty trlglycerldes in the presence of a catalyst selected from the group consisting of tr1l1th1um phosphate, trisodlum phosphate, tr1potassium phosphate, tetrasodlum pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodiu tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium basic alum1nos1Hcates, and potassium basic alumlnosHlcates, and mixtures thereof. The amount of catalyst 1s 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 Q molar basis. The reaction 1s preferably carried out at from about 138*C to about 170*C for typically from about 20 to about 90 minutes. When trlglycerldes are utilized 1n the reaction mixture as the fatty ester source, the reaction 1s also preferably carried out using from about 1 to about 10 weight % of a phase transfer 5 agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosldes, linear glycamlde surfactant, and mixtures thereof.
Preferably, this process 1s carried out as follows: 0 (a) preheating the fatty ester to about 138*C to about 170*C; (b) adding the N-alkyl or N-hydroxyal yl glucamine to the heated fatty add ester and mixing to the extent needed to form a two-phase 11quid/11quid mixture; 5 (c) mixing the catalyst Into the reaction mixture; and (d) stirring for the specified reaction time. Also preferably, from about 2% to about 20% of preformed linear H-alkyl/N-hydroxyalkyl, N-11near glucosyl fatty add amide product Is added to the reaction mixture, by weight of the 0 reactants, as the phase transfer agent 1f the fatty ester 1s a triglycerlde. This seeds the reaction, thereby Increasing reaction rate. A detailed experimental procedure is provided below in the Experimental.
The polyhydroxy "fatty add* amide materials used herein also 5 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.
In one particularly preferred embodiment of the invention the polyhydroxy fatty acid amide materials are sourced from tallow fat such that R.2 is a C15-C17 straight chain alkyl group.
It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), 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. Preferably, 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 compositions 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.
The polyhydroxy fatty acid amide component is present at a level of at least 1% by weight of the composition, more preferably at a level of from 1% to 10% by weight and most preferably at a level of from 2% to 6% by weight.
Nonionic Surfactants
Laundry detergent compositions of the present invention comprise, in addition to the polyhydroxy fatty acid amide component, one or more of the nonionic surfactants described herein. The nonionic surfactants described herein will hereinafter by referred to as "additional nonionic surfactants." Nonionic compounds other than these additional nonionic surfactants may be optionally included in the nonionic surfactant system of the present invention. These other, optional nonionic compounds will hereinafter be referred to as "optional nonionics." Without intending to be limited thereby, it is believed that when such optional nonionics are included in the nonionic surfactant system of the present invention, they do not provide the unexpected stain-removal benefits already described herein.
Additional Nonionic Surfactants
Primary C11-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol comprise the additional nonionic surfactants useful in compositions of the present invention. Such alcohol ethyoxylates should have an ethylene oxide content of less than 50% by weight and should be water insoluble.
A preferred aliphatic alcohol ethoxylate is a linear or substantially linear aliphatic alcohol containing an average of 12-15 carbon atoms in the alkyl chain, ethoxylated with an average of three ethoxy groups per mole of alcohol.
The additional nonionic surfactant is present at a level of at least 1%, preferably from 1% to 10% and more preferably from 1% to 6% by weight of the composition.
The third essential component of laundry detergent compositions in accordance with the invention is one or more water soluble surfactants selected from anionic, cationic, ampholytic and zwitterionic surfactants.
Anionic Surfactants
The laundry detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present invention, one or more anionic surfactants as described below.
AI YI Ester ■■If.n.te Surfactant
Alkyl ester sulfonate surfactants hereof Include linear esters of C8- 20 carboxylic adds (I.e., fatty adds) 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 oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
0 R3. CH - C - OR*
I SO3M wherein R3 1S a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R* is a C_-Cβ hydrocarbyl, preferably an alkyl, or combination thereof, and H 1s a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations Include metals such as sodium, potassium, and llthrum, and substituted or unsubstltuted ammonium cations, such as monoethanolamine, d1ethanolamine, and tr1ethanolamine. Preferably, R3 is C_Q-Ci6 alkyl, and R* 1s methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R31S Cio-Ciβ alkyl. Alkvl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M 1s H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimβthyl ammonium) cations and quaternary aπrnonium cations such as tetramethyl -ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from al kyl amines such as ethyl amine, di ethyl amine, tri ethyl amine, and mixtures thereof, and the l ike) .
Alkyl chains of 12-16 carbon atoms, more preferably 14-15 carbon atoms are preferred.
Al -vl Al kmrvl atad Sulfate Surfactant
Al kyl alkoxylated sul fate surfactants hereof are water sol uble salts or adds of the formula R0(A)mS03M wherein R is an unsubstltuted C10-C24 al kyl or hydroxyal kyl group having a C10-C24 al kyl component, preferably a C12-C20 alkyl or hydroxyalkyl , more preferably an alkyl group having from 12 to 18 carbon atoms, especially from 12 to 15 carbon atoms.
A is an ethoxy or propoxy unit, ra 1s 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-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations Include methyl-, dimethyl-, tr1methyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, d1ethylamine, tr1ethylamine, mixtures thereof, and the like.
Preferredexamples ofalkylalkoxylatedsulfatesurfactants are the C12- 18 alkyl ethoxy sulfates containinganaverage ofup to three ethoxygroupspermole ofalkyl ethoxy sulfate.
A particularly preferred surfactant is Ci2-Cl5 a^Y*i polyethoxylate (3.0) sulfate (C12- 5 E(3.0)M). Other exemplary surfactants include C12- 8 alkyl polyethoxylate (1.0) sulfate (C12-C18 E(l.O)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-Ci8E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (Ci2-CιβE(3.0)M), and C12-C18 alkyl polyethoxyl te (4.0) sulfate (Ci2-Ci8E(4.0)M), wherein M is conveniently selected fross sodium and potassium. Ωther Anionic Surfactants
Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can Include salts (Including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, d1- and tr1ethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, C8-C24 oleflnsulfonates, sulfonated polycarboxyϋc adds prepared by sulfona ion of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, 8-C24 alkylpolyglycolethersvlfates (containing up to. 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol su fonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, 1seth1onates such as the acyl 1seth1onates, N-acyl taurates, alkyl sucdnamates and sulfosucdnates, monoesters of sulfosucdnates (especially saturated and unsaturated C12-C18 monoesters) and dlesters of sulfosucdnates (especially saturated and unsaturated C5-C12 dlesters), acyl sarcoslnates, sulfates of alkylpolys cchar- ides such as the sulfates of alkylpolyglucosidβ (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)|cCH2COO-M+ wherein R 1s a C8-C22 alkyl, k Is an Integer from 0 to 10, and M 1s a soluble salt-forming cation. Resin adds and hydrogenated resin adds are also suitable, such as rosin, hydrogenated rosin, and resin adds and hydrogenated resin adds present 1n or derived from tall oil. Further examples are described 1n "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 Laugh!in, et al. at Column 23, l ine 58 through Column 29, l ine 23 (herein Incorporated by reference).
Preferred anionic surfactant systems employed in the laundry detergent compositions of the invention are free of alkyl benzene sulfonate salts. A highly preferred system comprises a mixture of a major proportion of a water-soluble C14-C15 alkyl sulfate and a minor proportion of a C12- 5 alkyl ethoxysulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. The laundry detergent compositions of the present invention typically comprise from about 1 % to about 20% , preferably from about 3 % to about 15% and most preferably from 5% to 10% by weight of anionic surfactants.
The laundry detergent compositions of the present Invention may also contain cationic, ampholytlc, zwUterionlc, and seal -polar surfactants
Cationic detersive surfactants suitable for use 1n the laundry detergent compositions of the present Invention are those having on* long-chain hydrocarbyl group. Examples of such cationic surfactants Include the amwmlusi surfactants such as alkyl dimethyl ammonium halogβnldβs, and those surfactants having the formula:
[R2(0R3)y] [l.4(0*3)y]2 5N*χ- whereln R& Is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoas In the alkyl chain, each R3 1S selected from, the group consisting of -CHsCI-tø-, -CH2CH(CH3)-, •CH2CH(CH2θH)-, -CH2CH2CH2-, and mixtures thereof; each R* Is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy¬ alkyl, benzyl ring structures formed by joining the two R4 groups, -CH2CH0H-CH0HCORβCHOHCH2θH wherein R* Is any hexose or hexose polymer having a molecular weight less: than about 1000, and hydrogen when y 1s not 0; R5. Is the saae- as R4 or 1s an alkyl chain wherein the total nuaber of carbon atoas of R2 plus R5 1s not more than about 18; each y Is frost 0 to about 10 and the sum of the y values Is from 0 to about 15; and X Is any compatible anion.. Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about 25%, preferably from about 3% to about 15% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocycllc secondary and tertiary amines in which the- aliphatic radical can be straight- or branched-chain. One of the aliphatic substltuents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubi11zing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No.3,929,678 to LaughUn et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants. When included therein, the laundry detergent compositions of the present Invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
Zw1tter1oπ1c surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocycllc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonlum or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to LaughUn 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.
When Included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such zwittarionic surfactants. 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
0
R3(0R4)XN(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R* 1s an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x 1s from 0 to about 3; and each R5 1S 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.
These amine oxide surfactants 1n particular Include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl d1hydroxy ethyl amine oxides.
When Included therein, the laundry detergent compositions of the present Invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants. ByHter.
The laundry detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control. The level of builder can vary widely depending upon the end use of the composition and Its desired physical form. Liquid formulations typically comprise at least about 1%, more typically froa 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%, preferably froa about 15% to about 50% by weight of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic detergent builders Include, but are not limited to, the alkali metal, ammonium and alkanolamaonlua salts of poly- phosphates (exemplified by the trlpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phy ic add, silicates, carbonates (Including blcarbonates and sesqul- carbonates), sulfates, and alualnoslHcates. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions canalsobeusedbutarenotpreferredatwashconditionslessthan about50°C, especiallylessthanabout40°C. Preferredbuilder systemsarealsofreeofphoβphatee.
Examples of silicate builders are the alkali metal silicates, particularly those having a ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodlua silicates. Preferred crystalline layered sodium silicates have the general formula
NaMSixθ2χ+ i yH2θ
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A- 3742043, incorporated herein by reference. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the < - -» β - Y - and - forms of Na2Si2θ5. These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is ^ - a2Si2θ5, NaSKS-6.
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.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-
carbonate and mixtures thereof with ultra-fine calcium carbona as disclosed in German Patent Application No. 2,321,001 publish on November 15, 1973, the disclosure of which is incorporat herein by reference. Aluminosilicate builders are especially useful in the prese invention. Aluminosilicate builders are of great importance most currently marketed heavy duty granular deterge compositions, and can also be a significant builder ingredient i liquid detergent formulations. Aluminosilicate builders inclu those having the empirical formula:
Mz(zA102-yS102) wherein M is sodium, potassium, ammonium or substituted ammoniu z is from about 0.5 to about 2; and y 1s 1; this material having magnesium ion exchange capacity of at least about 50 milligra equivalents of CaC03 hardness per gram of anhydrous alumino silicate. Preferred**alurainos11lcates are zeolite builders whic have the formula:
Naz[(A102)z(S102)y]-xH20 wherein z and y are integers of at least 6, the molar ratio of to y 1s in the range from 1.0 to about 0.5, and x is an intege from about 15 to about 264.
Useful aluminosilicate 1on exchange materials ar commercially available. These alumlnoslHcates can be crystallin or amorphous in structure and can be naturally-occurring alumino silicates or synthetically derived. A method for producin aluminosilicate ion exchange materials 1s disclosed in U.S. Paten 3,985,669, Krumael, et al., Issued October 12, 1976, incorporate herein by reference. Preferred synthetic crystalline alumino silicate ion exchange materials useful herein are available unde the designations Zeolite A, Zeolite P (B), and Zeolite X. In a especially preferred embodiment, the crystalline aluminosilicat ion exchange material has the formu a:
Nai2[(A102)l2(S102)i2]-xH2O wherein x is from about 20 to about 30, especially about 27. This material 1s known as Zeolite A. Preferably, 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.
Examples of phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-l,l-d1phosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic add 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 benzylmethylIdene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Oleh ; U.S. Patent No. 3,422,021 Issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 Issued September 3, 1968, and January 14, 1969 to Quimby, said disclosures being incorporated herein by reference.
Polycarboxylate builder can generally be added to the composition in add form, but can also be added in the form of a neutralized salt. When utilized in salt form, 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 poly- carboxylatβ builders encompasses the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates Include oxydlsucdnate, as disclosed in Berg, U.S. Patent 3,128,287, Issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, Issued January 18, 1972, both of which are Incorporated herein by reference. A specific type of ether polycarboxyl tes useful as builders in the present invention also include those having the general formula:
CH(A)(C00X)-CH(C0OX)-O-CH(C0OX)-CH(COOX)(B) wherein A is H or OH; B is H or -0-CH(C00X)-CH2(C00X); and X is H or a salt-forming cation. For example, if in the above general formula A and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -0-CH(C00X)-CH2(C00X), then the compound is tartrate dlsuccinlc acid (TDS) and its water-soluble salts. Mixtures of these builders are especially preferred for use herein. Particularly preferred are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97:3 to about 20:80. These builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.
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 hydroxypolycarboxylates represented by the structure:
H0-[C(R)(C0OM)-C(R)(C0OM)-O]n-H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonlua cation, n 1s froa about 2 to about 15 (preferably n is froa about 2 to about 10, more preferably n averages from about 2 to about 4) and each R 1s the same or different and selected from hydrogen, C\.* alkyl or Ci-a substituted alkyl (preferably R is hydrogen).
Still other ether polycarboxylates include copolymers of πaleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-tr_1hydroxy benzene-2, 4, 6-tr1sulfonic add, and carboxymethyl- oxysuccinic acid. Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of poly- acetic acids. Examples of polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid, succinlc add, polymalelc add, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxyllc add, and carboxymethyloxysuccinic acid, and soluble salts thereof.
Citric builders, e.g., dtric 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.
Other 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 laundry detergent compositions of the present invention are the 3,3-d1carboxy-4-oxa-l,6-hexaned1oates and the related compounds disclosed 1n U.S. Patent 4,566,984, Bush, issued January 28, 1986, Incorporated herein by reference. Useful succinic acid builders Include the C5-C20 alkyl succinlc acids and salts thereof. A particularly preferred compound of this type Is dodecenylsucdnlc add. Alkyl succinlc adds typically are of the general formula R-CH(COOH)CH2(COOH) I.e., derivatives of succinic add, wherein R 1s hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described 1n the above-mentioned patents.
The sucdnate builders are preferably used in the form of their water-soluble salts, Including the sodium, potassium, ammonium and alkanolammonium salts. Specific examples of sucdnate builders include: lauryl- sucdnate, myristylsucdnate, palaltylsuc nate, 2-dodecenyl- sucdnate (preferred), 2-pentadecenylsucdnate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Examples of useful builders also include sodium and potassium carboxy ethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo- hexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dlspersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal carboxy- lates 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 polymerization conditions, an ester of glyoxylic add 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 1n 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 homo- and copolymers of aliphatic carboxylic adds such as maleic add, itaeon1c add, mesaconlc add, fu arlc add, aeonitic add, dtraconlc add.and methylenemalon1c add.
Other organic builders known in the art can also be used. For example, monocarboxyllc adds, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of C10-C 0 are typically utilized. The hydrocarbyls can be saturated or unsaturated.
___L_______i Detersive enzymes can be Included In the laundry detergent compositions of the present invention 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, Upases, 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.
Suitable examples of proteases are the subtil1s1ns which are obtained from particular strains of B.subtil1s and B.licheniforms. Another suitable protease 1s 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 1n British patent specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available Include those sold under the tradenames ALCALASE™ and SAVINASE™ by Novo Industries A/S (Denmark) and MAXATASE™ by International B1o-Synthet1cs, Inc. (The Netherlands).
Of Interest 1n the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A and methods for Its preparation are described 1n European Patent Application 130,756, published January 9, 1985, Incorporated herein by reference. Protease B 1s a proteolytic enzyme which differs from Protease A in that 1t has a leudne substituted for tyrosine in position 217 1n Its amino add sequence. Protease B Is described in European Patent Application Serial No. 87303761.8f 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.
(*see page 57A for Equivalent Application) 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. Amylolytlc proteins include, for example, RAPIDASE™, International Bio-Synthetics, Inc. and TERMAMYL™, 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. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, Incorporated herein by reference, which discloses fungal cellulase produced from Hum1cola insolβns. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2.247.832. Examples of such cellulases are cellulases produced by a strain of Humlcola Insolens (Huaicola grlsea var. thermoidea), particularly the Humlcola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeroaonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabβlla Auricula Sol nder). Suitable Upasβ enzymes for detergent usage Include those produced by microorganisms of the Pseudoaonas group, such as Pseudoaonas stutzerl ATCC 19.154, as disclosed 1n British Patent No. 1,372,034, Incorporated herein by reference. Suitable Upases Include those which show, a positive laaunologlcal cross-reaction with the antibody of the llpase, produced by the microorganism Pswdomoπis fluortsctns IAM 1057. This llpase and a method for Its purification have been described 1n Japanese Patent Application No. 53-20487, laid open to public Inspection on February 24, 1978. This llpase Is available froa Aaano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Llpase P "Aaano," hereinafter referred to as "Aaano-P." Such Upases of the present Invention should show a positive laaunologlcal cross reaction with the Aaano-P antibody, using the standard and well-known 1maunod1ffusion procedure according to Ouchtsriony (Acta. Med. Scan., 133, pages 76-79 (1950)). These Upases, and a method for their 1mmuno1og1cal cross-reaction wi Amano-P, are also described in U.S. Patent 4,707,291, Thorn et al. Issued November 17, 1987, incorporated herein by referenc Typical examples thereof are the Amano-P Upase, the lipase PseudonoMS frigl PERM P 1339 (available under the trade na .Amano-8), Upase ex Psu*doaon»s nitrortductns var. l ipolytic FERM P 1338 (available under the trade name Aaano-CES), Upases e C romobtcter viscosuM, e.g. Chromobtcfr viseosua var. l ipolyticu NRRLB 3673, commercially available froa Toyo Jozo Co., Tagata Japan; and further Chromobtc r vlscosu Upases froa U.S Biochemical Corp., U.S.A. and Dlsoynth Co., The Netherlands, an lipases ex Pseudomonas gladioli. An especially preferred lipase enzyme is manufactured and sold by Novo Industri A/S,Denmark, under the trade name Lipolase (Biotechnology Newswatch, 7 March 1988, page 6) and mentioned, along with other suitable lipases, in EP O 258068 (Novo), incorporated herein by reference.
Peroxidasβ enzymes are used 1n 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. Peroxidasβ enzymes are known 1n the art, and Include, for example, horseradish pβroxidasβ, Hgnlnase, and haloperoxldase such as chloro- and bromo-pβroxidasβ. Perox1dase-conta1n1ng detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by 0. K1rk, assigned to Novo Industries A/S, Incorporated herein by reference. A wide range of enzyae materials and means for their Incorporation Into synthetic detergent granules 1s also disclosed in U.S. Patent 3,553,139, Issued January 5, 1971 to McCarty et al. (Incorporated herein by reference). Enzymes are further disclosed In U.S. Patent No. 4,101,457, Place et al.. Issued July 18, 1978, and 1n U.S. Patent 4,507,219, Hughes, Issued March 26, 1985, both Incorporated herein by reference. Enzyae materials useful fo liquid detergent formulations, and their Incorporation into such formulations, are disclosed 1n U.S. Patent 4,261,868, Hora et al., issued April 14, 1981, also Incorporated herein by reference. Enzyaβs are normally Incorporated at levels sufficient to provide up to about 5 ag by weight, more typically about 0.05 mg to about 3 ag, of active enzyae per graβ of the composition. For granular detergents, the enzymes are preferably coated prilled with additives inert toward the enzymes to minimize du formation and improve storage stability. Techniques f accomplishing this are well known in the art. In liqu formulations, an enzyme stabilization system is preferab utilized. Enzyme stabilization techniques for aqueous deterge compositions are well known in the art. For example, o technique for enzyme stabilization in aqueous solutions involv the use of free calcium ions from sources such as calcium acetat calcium formate, and caldum propionate. Calcium ions can be us in combination with short chain carboxylic add salts, preferabl formates. See, for example, U.S. Patent 4,318,818, Letton, al., issued March 9, 1982, incorporated herein by reference. I has also been proposed to use polyols like glycerol and sorbitol Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvale alcohols with polyfunctional aliphatic amines (e.g., alkanolamine such as diethanolamine, triethanolamine, dl-isopropanolamine etc.), and boric add or alkali metal borate. Enzym stabilization techniques are additionally disclosed an exemplified in U.S. Patent 4,261,868, issued April 14, 1981 t Horn, et al., U. S. Patent 3,600.319, issued August 17, 1971 t Gedge, et al., both incorporated herein by reference, and Europea Patent Application Publication No. 0 199 405, Application No 86200586.5, published October 29, 1986, Venegas. Non-boric aci and borate stabilizers are preferred. Enzyae stabilizatio systeas are also described, for example, in U.S. Patent 4,261,868, 3,600,319, and 3,519,570. Bleaching Compounds - Bleaching Aoents and Bleach Activators
The laundry detergent compositions of the present inventio may contain bleaching agents or bleaching compositions containin bleaching agent and one or more bleach activators. When included, present bleaching compounds will typically comprise from about 1 to about 20X, more typically froa about 1% to about 10%, of suc laundry detergent composition. In general, bleaching compounds are optional components in non-11quid formulations, e.g., granula detergents. If present, the amount of bleach activators will typical ly be from about 0.1% to about 60%, more typical ly fro about 0.5% to about 40% of the bl eaching composition .
The bleaching agents used herein can be any of the bleachin agents useful for detergent compositions 1n textil e cl eaning, har surface cleaning, or other cleaning purposes that are now known o become known.
One category of bleaching agent that can be used encompasses percarboxyl lc add bleaching agents and salts thereof. Suitable examples of this class of agents Include agneslua monoperoxy- phthalate hβxahydratβ, the eagneslua salt of aeta-chloro perbenzolc add, 4-nonylaa1no-4-oxopβroxybutyr1c add and diperoxydodecanedlolc ac d. Such bleaching agents are disclosed
1n U.S. Patent 4,483,781, Hartaan, Issued Noveaber 20, 1984, U.S.
Patent Appl ication 740,448* Burns et al . , filed June 3, 1985, European Patent Application 0,133,354, Banks et al . , publ ished
February 20, 1985, and U.S. Patent 4,412,934, Chung et al . , issued
Noveaber 1, 1983, all of which are Incorporated by reference herein. Highly preferred bleaching agents also Include 6-nonyl - aa1no-6-oxopβroxycapro1c add as described 1n U.S. Patent 4,634,551, Issued January 6, 1987 to Burns, et al . , Incorporated herein by reference.
The laundry detergent compositions of the present invention will generally include a peroxygen bleaching agent, usually an inorganic perhydrate bleach, normally in the form of the sodium salt.
Suitable perhydrate bleaches may be any of the inorganic salts such as. perborate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal normally sodium, perborate or percarbonate. Sodium perborate can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate
Sodium percarbonate, which is the preferred perhydrate, is an addition compound having a formula corresponding to
2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, l-hydroxyethyiidene,
(*see page 57Δ for Equivalent Application) 1, 1 -diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated into detergent compositions during the manufacturing process. Although the percarbonate can be incorporated into detergent compositions without additional protection, preferred executions of such compositions utilise a coated form of the material. A variety of coatings can be used, but the most economical is sodium silicate of Siθ2:Na2θ ratio from 1.6: 1 to
3.4:1, preferably 2.8:1, applied as an aqueous solution 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 included in the coating.
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.
A wide range of bleach activators can be used, examples being disclosed in Spadini et al USP 4179390. Preferred bleach activators include the tetraacetyi alkylene diamines, particularly tetraacetyl ethylene cLiamine (TAED) and tetraacetyl glycouril (TAGU).
0
I! R - C - L wherein 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 froa about 6 to about 10 carbon atoas and L is a leaving group, the conjugate acid of which has a pK« 1n the range of froa about 4 to about 13. These bleach activators are described 1n 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 1n the art and can be utilized herein. One type of non- oxygen bleaching agent of particular Interest includes photo- activated bleaching agents such as the sulfonated zinc and/or alualnua phthalocyaninβs. These materials can be deposited upon the substrate during the washing process. Upon Irradiation with light, In the presence of oxygen, such as by hanging clothes out to dry 1n the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate Is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al., incorporated herein by reference. Typically, detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine. Polymeric Soil Release Aoent
Any polymeric soil release agents known to those skilled in the art can be employed in the laundry detergent compositions of the present invention. Polymeric soil release agents are characterized by having both hydrophllic segments, to hydrophilize the surface of hydrophoblc fibers, such as polyester and nylon, and hydrophoblc 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 hydrophllic 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 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 Methocel** (Dow).
Cellulosic soil release agents also Include those selected froa the group consisting of C1-C4 alkyl and Ca hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcel ulose, and hydroxybutyl methylcellulose. A variety of cellulose derivatives useful as soil release polymers are disclosed 1n 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(vlnyl ester), e.g., Ci-Cβ vinyl esters, preferably poly(v1nyl acetate) grafted onto polyal ylene oxide backbones, such as polyethylene oxide backbones. Such materials are known in the art and are described in European Patent Application 0219048, published April 22, 1987 by ud, et al. Suitable commercially available soil release agents of this kind include the Sokalan™ type of material, e.g., SokalanTH HP-22, available from BASF (West Germany).
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 55,000. See U.S. Patent 3,959,230 to
Hays, issued Hay 25, 1976, which 1s incorporated by reference.
See also U.S. Patent 3,893,929 to Basadur Issued July 8, 1975
(Incorporated by reference) which discloses similar copolymers.
Another preferred polymeric soil release agent 1s 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. Examples of this polymer include the commercially available material ZelconR 5126 (from Oupont) and H1leaseR T (from ICI). These polymers and methods of their preparation are more fully described 1n U.S. Patent 4,702,857, Issued October 27, 1987 to Gossβlink, which 1s Incorporated herein by reference.
Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomerlc ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from ally! alcohol ethoxylate, dimethylterephthalate, and 1,2 propylene diol, wherein 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 4968451, issued 6 November1990 to J. J. Scheibel and E. P. Gosselink, U.S. Serial No. 07/474,709, filed January 29, 1990, incorporated herein by reference.
Other suitable polymeric soil release agents include the ethyl- or methyl-capped 1,2-propylene terephthalate-polyoxy- ethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., the anionic end-capped ollgomeric 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. 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 1s a C1-C4 alkyl, or preferably methyl, all of these patents being Incorporated herein by reference. Additional soil release polymers include the soil release polymers of U.S. Patent 4,877,896, Issued October 31, 1989 to Haldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being Incorporated herein by reference. The terephthalate esters contain unsymmetHcally substituted oxy-l,2-a1ky1eneoxy units.
If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, preferably from about 0.1% to about 5.0%,.more preferably froa about 0.2% to about 3.0% by weight of the laundry detergent compositions of the present Invention. Chelatinα Aoents
The laundry detergent compositions of the present invention may also optionally contain one or more Iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected froa the group consisting of amino carboxylates, amino phosphonates, polyfunctlonally-substHuted aromatic chelating agents and alxtures 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 ex¬ ceptional 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 - CH2 \ N - (CH2)X - COOM,
/ wherein H is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, pref¬ erably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Operable amine carboxylates include ethy1enediaminetetraacet tes, N-hydroxyethylethylenediaminetriacetates, nitri1otriacetates, ethylened1amine tetraproprionates, triethylenetetraaminehexa- acetates, diethylenetriaminepentaacetates, and ethanoldiglydnes, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the laundry detergent compositions of the present Invention when at least low levels of total phosphorus are permitted 1n detergent compositions. Compounds with one or more, preferably at least two, units of the substructure - CH2 \ N - (CH2)X - PO3M2, / wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x 1s from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakls (methylenephosphonates), nitrllotrls (methylenephosphonates) and dlethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbo atoms. Alkylene groups can be shared by substructures.
Polyfunctionally-substituted aromatic chelating agents ar also useful in the compositions herein. These materials ca comprise compounds having the general formula
OH
wherein at least one R is -SO3H or -COOH or soluble salts thereo and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al., incorporated herein by reference, disclose polyfunctlonally - substituted aromatic chelating and sequesterin agents. Preferred compounds of this type in acid form ar dlhydroxydlsulfobenzenes such as l,2-d1hydroxy-3,5-d1sulfobenzene. Alkaline detergent compositions can contain these materials in th form of alkali metal, ammonium or substituted ammonium (e.g. ono-or triethanol-amine) salts. If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions of the present Invention. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight o such compositions. Clav Soil Removal/Ant1-redepos1t1on Aoents
Clay soil removal/ant1-redepos1t1on agents useful in the laundry detergent compositions of the present Invention include polyethylene glycols and water-soluble ethoxylated amines having clay soil removal and antl-redeposltlon properties. Polyethylene glycol compounds useful 1n the laundry detergent compositions of the present Invention typically have a molecular weight 1n the range of from about 400 to about 100,000, preferably froa about 1,000 to about 20,000, more preferably from about 2,000 to about 12,000, most preferably froa about 4,000 to about 8,000. Such compounds are commercially available and are sold as Carbowax*, which is available from Union Carbide, located in Danbury, Conn.
The water-soluble ethoxylated amines are preferably selected from the group consisting of: (1) ethoxylated monoa ines having the formula:
(2) ethoxylated diamines having the formula:
R2-N-R1-N-R2 (R2)2_N-R1-N-(R2)2 L L L X X X or
(3) ethoxylated polyamines having the formula:
R2 R3-[(Al)q-(R*)t-N-L-X]p
(4) ethoxylated amine polymers having the general formula:
R2
[(R2)2-N3w_Rl-N3χ.Rl-N.ytRl-N-L-X)z
L X and
(5) mixtures thereof; wherein Al is
0 0 0 0 0 ιι Ii M it ft
-NC- , -NC0- , -NCN- , -CN- , -OCN-, R R R R R R
0 0 0 0 0
I I H [I ii I I
-CO-, -0C0- , -0C- , -CNC- ,
I
R or -0-; R 1s H or C1-C4 alkyl or hydroxyalkyl; Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, 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 R21s C1-C4, or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r» -A2-(CH2)S-. "herein A is -0- or -CH2-, r is l 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; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites; R* is C1-C alkylene, hydroxyalkylene,. alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or 0-N bonds are formed; L is a hydrophiϋc chain which contains the polyoxyalkylene moiety -_(R50)m(CH2CH2θ)n]-, wherein ≠ is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH CH2θ)n- comprises at least about 50% by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and n is at least about 12; for said dia ines, 1s from 0 to about 3, and n is at least about 6 when R is C2-C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m 1s from 0 to about 10 and n is at least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t 1s 1 when q 1s 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2. The most preferred soil release and ant1-redeposit1on agent is ethoxylated tetraethylenepentamine. 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. Other clay soil removal/ant1-redepos1t1on agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionlc 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.
The most preferred soil release and ant1-redepos1t1on agents are ethoxylated tetraethylenepentamine and the polyethylene glycols having a molecular weight 1n the range of from about 4,000 to about 8,000. Granular detergent compositions which contain such compounds typically contain from about 0.01% to about 10.0% by weight of the clay removal agent; liquid detergent compositions typically contain from about 0.01% to about 5.0% by weight. Polymeric Dispersing Aoents
Polymeric polycarboxylate dispersing agents can advantageously be utilized in the laundry detergent compositions of the present invention. These materials can aid in calcium and magnesium hardness control. In addition to acting as a builder adjunct analogously to the polycarboxylate described above in the Builder description, it 1s believed, though it 1s not intended to be limited by theory, that these higher molecular weight dispersing agents can further enhance overall detergent builder performance by inhibiting crystal growth of inorganics, by particulate soil peptization, and by antiredepositions, when used in combination with other builders including lower molecular weight pol carboxyl tes.
The polycarboxylate materials which can be employed as the polymeric polycarboxylate dispersing agent are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula X Z
COON
wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxy- methyl; a salt-forming cation and n is from about 30 to about 400. Preferably, X is hydrogen or hydroxy, Y 1s hydrogen or carboxy, Z is hydrogen and M is hydrogen, alkali metal, ammonia or substituted ammonium.
Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolyerlzing suitable unsaturated monomers, preferably in their add form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric poly- carboxylates include acrylic add, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalon1c acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. 1s suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic add. Such acrylic add-based polymers which are useful herein are the water-soluble salts of polymerized acrylic add. The average molecular weight of such polymers in the add form ranges from about 2,000 to 10,000, more preferably froa about 4,000 to 7,000 and most preferably froa about 4,000 to 5,000. Water-soluble salts of such acrylic add ho opoiymers Include, for example, the alkali metal, amaonlua and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type 1n detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967. This patent 1s Incorporated herein by reference.
Acryllc/malβic-based copolymers may also be used as a preferred component of the dispersing agent. Such materials include the water-soluble salts of copolymers of acrylic add and maleic acid. The average molecular weight of such copolymers in the add form ranges froa about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably froa about 7,000 to 60,000. The ratio of aerylate to aaleate segaents 1n such copolymers will generally range froa about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic add/ maleic add copolymers can Include, for exaaple, the alkali metal, amaonlua and substituted aaeonlua 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 1s Incorporated herein by reference. If utilized, the polymeric dispersing agents will generally comprise from about 0.2% to about 10%, preferably from about 1% to about 5% by weight of the laundry detergent compositions. Brightener Optical brighteners or other brightening or whitening agents known to those skilled in the art can be incorporated into the laundry detergent compositions of the present Invention. However, the choice of brightener 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 1s 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. Commercial optical brighteners can be classified into subgroups which Include, but are not necessarily limited to, derivatives of stilbene, pyrazollne, couraarin, carboxylic acid, methlnecyanlnes, d1benzoth1phene-5,5-d1ox1de, azoles, 5- and 6-meabered-r1ng heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnlk, Published by John Wiley & Sons, New York (1982), the disclosure of which Is Incorporated herein by reference.
Stilbene derivatives Include, but are not necessarily limited to, derivatives of bis(tr1az1nyl)amino-stilbene; bisacylamino derivatives of stilbene; trlazolβ derivatives of stilbene; oxadlazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
Certain derivatives of b1s(tr1az1nyl)am1nost1lbene may be prepared from 4,4'-d1amine-stilbene-2,2'-d1sulfonic acid. Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-positioπ, and in the 3- and 7-positions.
Carboxylic acid derivatives 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 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 Zahradnlk reference.
The styrylazoles can be further subclassified into styryl- benzoxazoles, styrylimldazoles and styrylth1azoles, as disclosed on page 78 of the Zahradnlk reference. It will be understood that these three Identified subclasses may not necessarily reflect an exhaustive 11st of subgroups into which styrylazoles may be subclassified. Other optical brighteners are the derivatives of d1benzoth1ophene-5,5-d1ox1de 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 1s Incorporated herein by reference, and include 3,7-d1am1nod1benzoth1ophene-2,8-d1su1fon1c add 5,5 dioxide.
Other optical brighteners are azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcategorized Into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk-Othmer reference.
Still other optical brighteners are the derivatives of 6-membered-ring heterocycles disclosed 1n the Kirk-Othmer reference. Examples of such compounds Include brighteners derived from-pyrazlne and brighteners derived froa 4-am1nonaphthalamide. In addition to the brighteners already described, miscellaneous agents may also be useful as brighteners. Examples of such miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include l-hydroxy-3,6,8-pyrenetri- sulfonic acid; 2,4-dimethoxy-l,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolonedisulfonic acid; and derivatives of pyrazoline- quinoline.
Other specific examples of optical brighteners 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. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from C1ba-Ge1gy; 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'-b1s-(l,2,3-tr1azol-2- yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the y-am1no- coumarins. Specific' examples of these brighteners include 4-methyl-7-diethylamino coumarln; l,2-b1s(-benz1midazol-2-yl)- ethylene; 1,3-diphenylphrazoHnes; 2,5-b1s(benzoxazol-2-yl)- thiophene; 2-styryl-naphth-[l,2-d]-oxazole; and 2-(stilbene-4-yl)- 2H-naphtho[l,2-d]triazole.
Still other optical brighteners Include those disclosed in U.S. Patent 3,646,015, Issued February 29, 1972 to Hamilton, the disclosure of which is Incorporated herein by reference.
If utilized, the optical brighteners will generally comprise from about 0.05% to about 2.0%, preferably from about 0.1% to about 1.0% by weight of the laundry detergent compositions. Suds Suppressors
Compounds known, or which become known, for reducing or suppressing the formation of suds can be Incorporated Into the laundry detergent compositions of the present Invention. The incorporation of such materials, hereinafter "suds suppressors," can be desirable because the polyhydroxy fatty add 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 polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic 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. A wide variety of materials may be used as suds suppressors. 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 monocarboxy1ic 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 monocarboxyl1c fatty adds, 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 laundry detergent compositions of the present invention may also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty add esters (e.g., fatty add trlglycerldes), fatty acid esters of monovalent alcohols, aliphatic 18-C 0 ketones (e.g. stearone), etc. Other suds Inhibitors Include N-alkylated amino trlazlnes such as tr1- to hexa-alkylmelamines or di- to tetra-alkyld1amine chlortrlazlnes 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, preferably 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 heterocycllc 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.
Another preferred category of non-surfactant suds comprises si11cone suds suppressors. This category includes the use of polyorganoslloxane oils, such as polydi ethylsiloxane, dispersions or emulsions of polyorganoslloxane oils or resins, and combinations of polyorganoslloxane with silica particles wherein the polyorganoslloxane 1s chemlsorbβd of fused onto the silica. SI11cone 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. Other s111cone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for defoaaing aqueous solutions by Incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of siHconβ and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. SiHcone defoaaers 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:
(1) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25*C; (11) from about 5 to about 50 parts per 100 parts by weight of
(1) of siloxane resin composed of (CH3)3 SiOι/2 units of Siθ2 units in a ratio of from (CH3)3 SIO1 2 units and to SIO2 units of from about 0.6:1 to about 1.2:1; and (111) from about 1 to about 20 parts per 100 parts by weight of
(1) of a solid silica gel;
Suds suppressors, when utilized, are present in a "suds suppressing amount." By "suds suppressing amount" is meant that the for ulator of the composition can select an amount of this suds controlling agent that will control the suds to the extent desired. The amount of suds control will vary with the detergent surfactant selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent 1s used to achieve the desired suds control than with low foaming surfactants. The laundry detergent compositions of the present invention will generally comprise froa 0% to about 5% of suds suppressor. When utilized as suds suppressors, aonocarboxyllc fatty adds, and salts, thereof, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor 1s utilized. SiHcone 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 primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably froa about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.255. to about 0.5%. As used herein, 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 generally utilized in amounts ranging from about 0.1% to about 2% by weight of the compositions.
Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. Other Ingredients
A wide variety of other ingredients which can be included in the laundry detergent compositions of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and iso- prcpanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,3-propanedlol) can also be used. The laundry detergent compositions of the present invention 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, alkali, adds, etc., and are well _known to those skilled 1n the art. _
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 containing the nonionic surfactant system of the present invention, wherein the weight ratio of polyhydroxy fatty acid amide to additional surfactant in the nonionic surfactant system is in the range of from about 1:5 to about 5:1, in the presence of a solvent such as water or a water-mi cible solvent (e.g., primary and secondary alcohols). Agitation is preferably provided for enhancing cleaning. Suitable means for providing agitation include rubbing by hand preferably with the aid of a brush, or other cleaning device, automatic laundry washing machines, automatic dishwashers, etc. gXPERI ENAL This exemplifies a process for making a N-methyl, 1-deoxy- glucityl lauramide surfactant for use herein. Although a skilled chemist can vary apparatus configuration, 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 1s Important in case of very rapid methanol evolution) to which 1s 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 1t may be readily raised or lowered to further control temperature of the reaction.
N-methylglucamine (195 g., 1.0 mole, Aldrlch, 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). When the melt temperature reaches 145* C, catalyst (anhydrous powdered sodium carbonate, 10.5 g., 0.1 mole, J. T. Baker) 1s added. The nitrogen sweep 1s 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.
Within 7 minutes, first methanol bubbles are sighted at the meniscus of the reaction mixture. A vigorous reaction soon follows. Methanol is distilled over until its rate subsides. The vacuum Is adjusted to give about 10 inches Hg. (10/31 a.m.) vacuum. The vacuum 1s Increased approximately as follows (in inches Hg. at minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of methanol evolution, heating and stirring are discontinued co-incident with some foaming. The product is cooled and solidifies.
The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the Invention, said scope being determined according to claims which follow.
The inventionis illustrated inthe following examples inwhichall amounts are byweightunless otherwise specified.
In the Examples, the abbreviated component identifications have the following meanings:
C12 AS Sodium linear C12 alkyl benzene sulfonate
TGA Glucityl tallow fatty acid amide TAS Sodium tallow alcohol sulfate C14/15AS Sodium C14-C15 alkyl sulfate
C12/I5AE3S Sodium C12-C15 aikyi ether sulfate containing an average of three moles of ethylene oxide per mole of alkyl sulfate
TAEr Tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol.
45E7 A C 14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide.
25E3 A C12-C15 primary alcohol condensed with an average of 3 moles of ethylene oxide.
TAED Tetraacetyl ethylene diamine Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio normally follows).
Carbonate Anhydrous sodium carbonate CMC Sodium carboxymethyl cellulose Zeolite A Hydrated Sodium Aluminosilicate of formula Nai2(Alθ2Si<_>2)i2. 7H2θ having a primary particle size in the range from 1 to 10 micrometers
Citrate Tri-sodium citrate dihydrate
MA/AA Copolymer of 1:4 maleic anhydride/acrylic acid, average molecular weight about 80,000.
Example I
The following particulate detergent compositions were prepared:
B C
6.5
6.5
The Performance of the three compositions was compared in both Tergotometer Tests and in full scale washing machine tests. Tergotometer Tests
6 x 2 litre metal pots were filled with water of 12° Clark Hardness (Ca:Mg = 4:1) and heated to 60°C. 14g of product was added to each pot and dissolved/dispersed to give a product weight concentration of 0.7%. Stained 7.5 cm x 7.5 cm cotton and polycotton fabric swatches were made by applying separate stripes of artificial sebum, shoe polish and dirty motor oil (DMO) uniformly on to each fabric swatch. A swatch of each fabric type was then attached to the paddle of each pot and the paddles were then agitated in the pots for 45 minutes. The total number of replicates for each product was 6. The swatches were then rinsed in cold water, dried overnight and then assessed by an expert panel using a five point Scheffέ scale. Washing Machine Tests
AEG Lavamat 980 automatic washing machines were used to carry out a similar comparison of the products. A 45 minute main wash cycle at 60 °C was selected and a product concentration of 0.7% in 12° Clark Hardness water (Ca:Mg = 4:1) was used. Six replicates for each product were carried out. Each wash load comprised 3kg of realistically soiled ballast fabrics composed of cotton sheets and towels together with polycotton items to give a cotton:polycotton weight ratio of approximately 3:1, together with sets of stained swatches.
The stain sets comprised:
2 greasy stains on cotton (lipstick, DMO).
2 greasy stains on polyester (make up, polish). After rinsing with cold water, each swatch was dried and then assessed by an expert panel using a five point Scheffέ scale.
The results of both test techniques are set out below.
The LH column shows the advantage for Composition A over Composition B while the RH column shows the advantage for Composition A over Composition C.
(s) = statistically significant at 95% confidence level.
Product C represents a prior art composition and the comparison A/C shows that composition A, in accordance with the invention,provides stain removal benefits relative to Composition C over a wide spectrum of soil types and fabrics. The comparison of compositions A&B shows the surprising benefit provided by the use of a combination in accordance with the invention relative to that provided by use of a higher level of the polyhydroxy fatty acid amide alone.
Example II
Composition A of Example I was compared to a commercially available detergent composition (D) which differed from Composition A only in that the 45AS, 25AE3S, TGA and 25E3 components were replaced by 7.6% C12 LAS, 3 % 45E7 and 1.1 % TAEn. The comparison was carried out in AEG Lavamat 980 washing machines using the wash conditions and procedure of Example 1 and a variety of stains on cotton, polycotton and polyester fabric swatches. Assessment of the washed fabric swatches by an expert panel using a five point Scheffe* scale showed that
Composition A provided a stain removal benefit over Composition D of
> 2 psu on polish froi-i polyester
> 1 psu on DMO from polycotton > 1.5 psu on make up from cotton
Example III
The performance of Composition A of Example I was compared to that of two further detergent Compositions D and E which differed from A only in that the 25E3 component was replaced by 68E3 and 68E5 respectively, where 68E3 and 68E5 are Ci6-Cχ8 predominantly linear primary alcohols condensed with an average of three and five moles of ethylene oxide respectively. The performance comparisons were made using the conditions and procedure of the tergotometer test of Example I.
.Assessment of the washed fabric swatches by an expert panel using a five point Scheffe'scale showed that Composition A, in accordance with the invention, provided significant stain removal benefits over both compositions D and E, neither of which is a composition in accord with the invention.
The results of the comparisons are set out below.
The LH column shows the advantage for Composition A over Composition D while the RH column shows the advantage for Composition A over Composition E.
A/D A/E Polycotton
- Sebum
- polish - DMO
Polyester
- sebum
- polish - DMO
s= statistically significant at 95% confidence level 57/1
(♦Equivalent Applications:)
USSN 07/578,760 = PCT/US91/06980 published as 092/06160 European Application No. 87303761.8 = European Patent 0,251,446, published 7 January 1988 USSN 740,446 = European Patent 0,170,386

Claims

- 58 -
1) A laundry detergent composition useful for cleaning fabrics in automatic washing machines, said composition comprising one or more water soluble anionic, cationic, ampholytic or zwitteronic detersive surfactants or mixtures thereof, and optionally detergent builder compounds, said composition being characterised in that it comprises, in combination,
(a) at least 1% by weight of the composition of a polyhydroxy fatty acid amide having the formula
O Ri
R2 — C N — Z
where Ri is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-C31 hydrocarbyl and Z is a poly hydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxy groups directly connected to said chain, or an alkyoxylated derivative thereof; and
(b) at least 1% by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50% by weight. - 59 -
2) A laundry detergent composition according to claim 1 wherein component a) is a polyhydroxy fatty acid amide of formula
R2— CH2(CHOH)4CH2OH
wherein R2 is a C\\-C\ straight chain alkyl or alkenyl group.
3) A laundry detergent composition according to either one of claims 1 or 2 wherein R2 is a C15-C19 straight chain alkyl or alkenyl group or a mixture thereof and Ri is methyl.
4) A laundry detergent composition according to any one of claims 1-3 wherein R2 is a C15-C17 straight chain alkyl group derived from tallow fat.
5) A laundry detergent composition according to any one of claims 1-4 wherein component b) comprises a linear or substantially linear aliphatic alcohol containing an average of 12-15 carbon atoms in the alkyl chain ethoxylated with an average of three ethoxy groups per mole of alcohol.
6) A granular laundry detergent composition according to any one of claims 1-5 comprising from 3% to 15% by weight of anionic surfactant, from 1% to 10% of component (a) and from 1% to 10% of component (b), the ratio of the weight of anionic surfactant to the combined weights of components a) and b) lying in the range from 1:3 to 3:1. - 60 -
7) A granular laundry detergent composition according to claim 6 wherein the anionic surfactant comprises water- soluble C12-C18 alkyl sulfates, C12-C18 alkyl ethoxy sulfates containing an average of up to three ethoxy groups per mole of alkyl ethoxy sulfate and mixtures thereof.
8) A granular laundry detergent composition according to claim 7 wherein the anionic surfactant is free of alkyl benzene sulfonate salts.
9) A granular laundry detergent composition according to any one of claims 6-8 wherein the anionic surfactant comprises a mixture of a major proportion, by weight of the mixture, of a water soluble C14-C15 alkyl sulfate and a minor proportion, by weight of the mixture, of a C12-
C15 alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.
10) A granular laundry detergent composition according to any one of claims 6-9 incorporating a non phosphate detergent builder system.
11) A granular laundry detergent composition according to claim 10 wherein the detergent builder is selected from synthetic crystalline or amorphous zeolite aluminosilicates, alkali metal carbonates, bicarbonates and organic polycarboxylates, alkali metal silicates, crystalline layered sodium silicates, water-soluble salts of acrylic acid homopolymers or acrylic acid copolymers with maleic anhydride, amino polycarboxylates and mixtures of any of the foregoing.
EP92914366A 1991-06-18 1992-06-11 Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol Expired - Lifetime EP0591397B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB919113139A GB9113139D0 (en) 1991-06-18 1991-06-18 Detergent compositions
GB9113139 1991-06-18
PCT/US1992/004902 WO1992022629A1 (en) 1991-06-18 1992-06-11 Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol

Publications (3)

Publication Number Publication Date
EP0591397A1 EP0591397A1 (en) 1994-04-13
EP0591397A4 true EP0591397A4 (en) 1995-10-04
EP0591397B1 EP0591397B1 (en) 1997-09-24

Family

ID=10696882

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Application Number Title Priority Date Filing Date
EP92914366A Expired - Lifetime EP0591397B1 (en) 1991-06-18 1992-06-11 Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol

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CN (1) CN1034083C (en)
AT (1) ATE158612T1 (en)
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BR (1) BR9206176A (en)
CA (1) CA2111592A1 (en)
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DK (1) DK0591397T3 (en)
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GB (1) GB9113139D0 (en)
GR (1) GR3024776T3 (en)
HU (1) HU213363B (en)
IE (1) IE921961A1 (en)
MX (1) MX9202991A (en)
NZ (1) NZ243178A (en)
PT (1) PT100605A (en)
TR (1) TR27927A (en)
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FR2693206B1 (en) * 1992-07-02 1994-09-16 Oreal Use in surfactant solutions of aminopolyol carbamates as thickeners and compositions containing them.
DE4323253C1 (en) * 1993-07-12 1995-01-05 Henkel Kgaa Use of fatty acid N-alkyl polyhydroxyalkylamides as rinse aid for machine cleaning hard surfaces
EP0709450A1 (en) * 1994-10-24 1996-05-01 The Procter & Gamble Company Low sudsing liquid detergent compositions
DE19524244C1 (en) * 1995-07-04 1997-02-20 Henkel Kgaa Nonionic surfactant concentrates
BR9814650A (en) * 1997-11-18 2000-12-26 Unilever Nv Powder detergent composition
EP3670495A1 (en) * 2018-12-21 2020-06-24 Clariant International Ltd Glucamide-based surfactants
CN116018394A (en) * 2020-08-26 2023-04-25 联合利华知识产权控股有限公司 Detergent compositions comprising isethionate surfactants

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Publication number Priority date Publication date Assignee Title
BE557103A (en) * 1956-05-14
DE1619087A1 (en) * 1967-08-14 1969-10-02 Henkel & Cie Gmbh Surfactant combinations which can be used as laundry detergents and detergents or auxiliary washing agents containing them
CA962158A (en) * 1971-03-11 1975-02-04 Unilever Limited Detergent compositions
US3925224A (en) * 1973-04-17 1975-12-09 Church & Dwight Co Inc Detergent additive composition
GB1516848A (en) * 1974-11-13 1978-07-05 Procter & Gamble Ltd Detergent composition
GB1569617A (en) * 1976-03-08 1980-06-18 Procter & Gamble Liquid detergent composition
DE3711776A1 (en) * 1987-04-08 1988-10-27 Huels Chemische Werke Ag USE OF N-POLYHYDROXYALKYL Fatty Acid Amides As Thickeners For Liquid Aqueous Surfactant Systems

Non-Patent Citations (1)

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Title
No further relevant documents disclosed *

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DE69222418D1 (en) 1997-10-30
BR9206176A (en) 1994-12-27
EP0591397A1 (en) 1994-04-13
NZ243178A (en) 1995-06-27
GR3024776T3 (en) 1997-12-31
IE921961A1 (en) 1992-12-30
AU2248292A (en) 1993-01-12
DE69222418T2 (en) 1998-04-16
ES2106877T3 (en) 1997-11-16
CN1069763A (en) 1993-03-10
HU9303643D0 (en) 1994-04-28
ATE158612T1 (en) 1997-10-15
JPH06508394A (en) 1994-09-22
CN1034083C (en) 1997-02-19
PT100605A (en) 1993-09-30
AU667047B2 (en) 1996-03-07
WO1992022629A1 (en) 1992-12-23
DK0591397T3 (en) 1998-03-09
HUT66843A (en) 1995-01-30
TR27927A (en) 1995-10-16
GB9113139D0 (en) 1991-08-07
HU213363B (en) 1997-05-28
CA2111592A1 (en) 1992-12-23
MX9202991A (en) 1993-02-01
EP0591397B1 (en) 1997-09-24
TW222308B (en) 1994-04-11

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