Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

• BACKGROUND Detergent formulators are typically faced with the task of devising products to remove a broad spectrum of soils and stains from fabrics. Such soils and stains are caused by use of the fabric prior to washing. However, many fabrics when washed become stained due to the wash environment. For example, some fabrics, especially white cottons, begin to turn yellow after repeated washings. Consequently, detergent formulators are faced with an additional task of not only removing existing stains, but preventing further staining caused by the wash environment.
• the present invention is directed to a laundry detergent composition
• a laundry detergent composition comprising a detersive surfactant and a terpolymer; wherein the terpolymer comprises at least a first monomeric unit comprising a weak acid function, a second monomeric unit comprising a strong acid function, and a third monomeric unit comprising a nonionic function.
• Such a detergent composition satisfies the need for a detergent composition which prevents the yellowing and/or maintains the whiteness of a fabric even after repeated washings.
• Alkyl means a carbon-containing chain, preferably from about C-j to about C ⁇ o- m °re preferably from about C ⁇
• Aralkyl means R'-R"-, wherein R' is an aryl and R" is an alkyl.
• Aryl means an aromatic; substituted (mono- or poly-) or unsubstituted, preferably unsubstituted. Preferred aryls are phenyl, puridyl, pyrmidyl and napthyl; more preferred is phenyl.
• “Comprising” means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms “consisting of and “consisting essentially of. "Cycloalkyl” means a cyclic alkyl (i.e., having one or more closed rings).
• Tepolymer refers to a polymer formed from three or more monomers.
• HMI heavy metal ions, and for purposes of discussion herein, includes Fe + 2, Fe +3 , Mn + 2, Mn + 3, Mn +4 , Cu +1 , Cu+2, Zn +2 and Pb + 2; and their oxide and hydroxide salts.
• Nonionic functional monomer refers to a monomer unit which doesn't have an ionic charge when placed in acidic, basic, or neutral solutions.
• “Strong acid functional monomer” refers to a monomer unit having one or more functional groups which completely dissociate in water. For example:
• Wash acid functional monomer refers to a monomer unit having one or more functional groups which only partially dissociate in water. For example:
• the present invention relates to a detergent composition
• a detergent composition comprising a detersive surfactant and a terpolymer; wherein the terpolymer comprises at least a first monomeric unit comprising a weak acid function, a second monomeric unit comprising a strong acid function, and a third monomeric unit comprising a nonionic function.
• these terpolymers have been found to be surprisingly efficacious in the maintenance of whiteness and/or prevention of yellowing of fabrics washed/rinsed in water containing HMI.
• the aspects and embodiments of the present invention set forth in this document have many surprising advantages, including maintaining the whiteness and/or preventing the yellowing of fabrics even after repeated washings.
• the terpolymer used in the present invention chelates the HMI in the wash and/or rinse water. Chelation is achieved when the polymer and/or chelant binds with the HMI through ion-ion interaction, the resulting complex remaining soluble in the water solution. It is also believed the terpolymer disperses HMI by "wrapping" itself around the HMI salts (e.g., Fe(OH)3), thereby preventing the insoluble HMI salts from adhering to the fabric.
• HMI salts e.g., Fe(OH)3
• compositions of the present invention are anti-proliferatives.
• a common problem found in detergent compositions comprising bleach is the decomposition of the bleach by HMI in the wash and/or rinse water. Consequently, chelants are added to detergent compositions comprising bleach to prevent such HMI from decomposing the bleach.
• the use of the terpolymers in the compositions of the present invention may additionally prevent or reduce bleach decomposition due to the chelant effects of the terpolymer. Consequently, this may reduce or eliminate the need to add additional "bleach protecting" chelants to the detergent composition.
• compositions of the present invention are the prevention of incrustation caused by, e.g., carbonates, silicate and/or orthophosphates, normally found in detergent compositions.
• carbonates form, e.g., calcium carbonate which, when deposited in fabric, may bestow a harsh or rough feeling to the fabric.
• the terpolymers used in the compositions of the present invention may prevent the deposition of such calcium carbonate by dispersing the calcium carbonate.
• a further possible benefit of the composition of the present invention is improved physical properties.
• the terpolymer bestows an additional benefit in which the composition has improved free flowing properties.
• Such free flowing properties improve processability during the manufacture and packaging of the detergent composition.
• Previously known detergent compositions i.e., those not containing the terpolymers of the present invention
• the terpolymers used in the compositions of the present invention have a powder form. Consequently, the terpolymer facilitates the free flow of the overall detergent composition through the processing line by preventing or reducing the frequency of clumping, caking or sticking of the detergent granules.
• the laundry detergent composition of the present invention may be in any suitable form, for example, high density liquids, light liquids or other pourable forms, granules, laundry bars, gels, or pastes.
• the terpolymers of the present invention can be formulated into any detersive matrix chosen by the formulator.
• the terpolymers used in the detergent compositions comprise a first monomeric unit, a second monomeric unit, and a third monomeric unit.
• other monomer units in addition to these three, may make up the terpolymer, so long as these additional monomers do not significantly interfere with the whitening maintenance and/or prevention of yellowing properties bestowed by the first, second and third monomeric units.
• the detergent composition comprises at least about 0.2% of the terpolymer.
• the terpolymer has a molecular weight of from about 500 to about 36,000 Daltons; more preferably from about 1 ,000 to about 20,000 Daltons; more preferably still, from about 3,000 to about 6,000 Daltons.
• the ratio of first monomeric unit to second monomeric unit to third monomeric unit in the terpolymer is from about 3:2:1 to about 8:6:5, more preferably from about 4:3:3 to about 8:1 :1 , more preferably still from about 5:3:2 to about 6:2:2.
• terpolymers useful in the present invention as well as synthesis of such terpolymers include those set forth in U.S. Patent 4,711 ,725, issued December 8, 1987.
• the first monomeric unit comprises a weak acid function.
• the first monomeric unit comprises a carboxylate function. More preferably, the first monomeric unit has the following structure
• R 1 is H or CH 3 , preferably H.
• R20 j s H or C(O)-OX.
• X is independently H, a metal cation or N-(R )4 wherein R is H, a C1-C4 hydroxyalkyl, or mixtures thereof; preferably X is H or Na + ; more preferably X is Na + .
• the first monomeric unit has the following structure
• R 7 is independently H or -COO- Z + ; preferably H.
• Z + is independently H or Na, preferably Na (i.e., -COO " Na + ).
• the second monomeric unit comprises a strong acid function.
• the second monomeric unit comprises a sulfonate function. More preferably the second monomeric unit has the following structure
• R 3 is H or CH3; preferably H.
• R 4 is H or C-1-C4 alkyl; preferably H or CH3; more preferably CH3.
• R ⁇ is C ⁇
• Y is H, a metal cation or N-(R 1)4; preferably H or Na + ; more preferably Na + .
• R 1 is H, a C1-C4 hydroxyalkyl, or mixtures thereof.
• the second monomeric unit has the structure
• R 8 is independently H or -COOH" Na + ; preferably H.
• R 9 is
• R10 is H or C1-C4 alkyl; preferably H or CH3; more preferably CH3.
• the third monomeric unit comprises a nonionic function.
• the third monomeric unit is a vinyl ester, vinyl acetate or substituted acrylamide; more preferably methyl substituted acrylamides.
• the vinyl ester has the structure 11
• R 1 is H or CH3; preferably H.
• R 1 is a C-
• R 13 is H or CH3; preferably H.
• R 14 is H or a C-
• n is an integer of from 1 to about 3; preferably 1.
• the vinyl acetate has the structure
• the substituted acrylamide has the structure H R 15
• R 15 is H or CH3; preferably H.
• R 16 and R 7 are independently H, a C1-C8 alkyl, a CQ-CQ cycloalkyl, a benzyl, or
• the third monomeric unit has the structure
• R 1 1 is independently H, -COO" H + - or -COO" Na + ; preferably H.
• R 2
• O II is — (CH2)qCH3, — (CH2)qOH, — C-O(CH 2 ) q CH 3 _ or
• q is independently from 0 to 6; preferably from about 0 to about 3; more preferably 1.
• R 13 and R 14 are independently — (CH2) CH3 or H.
• m is from 0 to about 6; preferably from about 0 to about 3; more preferably 0.
• the detergent composition also comprises a detersive surfactant.
• a detersive surfactant Preferably the detergent composition comprises at least about 0.01% of a detersive surfactant; more preferably at least about
• detersive surfactants are cationic, anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, further described herein below.
• detersive surfactants useful in the detergent composition include, the conventional C-
• the conventional nonionic and amphoteric surfactants such as the C ⁇
• 8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides.
• sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C ⁇ rj-C ⁇ i8 N-(3-methoxypropyl) glucamide.
• 8 glucamides can be used for low sudsing.
• C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C Q-C ⁇ Q soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
• the detergent compositions herein may optionally comprise other known detergent cleaning components including alkoxylated polycarboxylates, bleaching compounds, brighteners, chelating agents, clay soil removal / anti-redeposition agents, dye transfer inhibiting agents, enzymes, enzyme stabilizing systems, fabric softeners, polymeric soil release agents, polymeric dispersing agents, suds suppressors.
• the detergent composition may also comprise other ingredients including carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions.
• Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units.
• the side-chains are of the formula -(CH2CH2O) m (CH2)nCH3 wherein m is 2-3 and n is 6-12.
• the side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure.
• the molecular weight can vary, but is typically in the range of about 2000 to about 50,000.
• Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% of the compositions herein, b.
• Bleaching Compounds - Bleaching Agents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
• the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
• Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
• bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1 , 1983.
• Highly preferred bleaching agents also include 6-nonylamino-6- oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.
• Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
• a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% of said particles being smaller than about 200 micrometers and not more than about 10% of said particles being larger than about 1 ,250 micrometers.
• the percarbonate can be coated with silicate, borate or water-soluble surfactants.
• Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.
• Peroxygen bleaching agents, the perborates, the percarbonates, etc. 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 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.
• NOBS nonanoyloxybenzene sulfonate
• TAED tetraacetyl ethylene diamine
• R 1 N(R5)C(O)R 2 C(O)L or R 1 C(O)N(R5)R2C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
• a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
• a preferred leaving group is phenyl sulfonate.
• bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido- caproyl)oxybenzenesulfonate, (6-decanamido- caproyhoxybenzenesulfonate, and mixtures thereof as described in
• Another class of bleach activators comprises the benzoxazin- type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
• a highly preferred activator of the benzoxazin-type is:
• Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
• R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
• Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines, or silicon. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
• the bleaching compounds can be catalyzed by means of a manganese compound.
• a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621 , U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
• Preferred examples of these catalysts include Mn ,V 2(u-O)3(1 ,4,7-trimethyl-1 ,4,7-triazacyclo- nonane)2(PFe)2, Mn lll 2(u-O) ⁇ (u-OAc)2(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2-(CIO4)2, Mn' V 4(u-O)6(1 ,4,7- triazacyclononane)4(CIO4)4, Mn lll Mn IV 4(u-O)-
• metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
• the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161 ; and 5,227,084.
• compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor, c.
• Brightener
• optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
• Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5- dioxide, azotes, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
• optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl- phenyl)-2H-napthol[1 ,2-d]triazoles; 4,4'-bis- (1 ,2,3-triazol-2-yl)- stilbenes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
• these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(-venzimidazol-2-yl)ethylene; 1 ,3-diphenyl- phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1 ,2- d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1 ,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein. d. Builders
• Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
• the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1 % builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from 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 or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquiearbonates), sulphates, and aluminosilicates.
• non-phosphate builders are required in some locales.
• compositions herein function surprisingly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
• silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
• NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
• Na SKS-6 silicate builder does not contain aluminum.
• NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A- 3,417,649 and DE-A-3,742,043.
• SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + ⁇ yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
• layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms.
• the delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
• Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
• carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
• Aluminosilicate builders are useful in the present invention.
• Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
• Aluminosilicate builders include those having the empirical formula: M z (zAIO 2 )y] xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
• aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AIO 2 )i2(SiO 2 )i2] xH2O wherein x is from about 20 to about 30, especially about 27.
• This material is known as Zeolite A.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
• polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
• Polycarboxylate builder can generally be added to the composition in acid 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, or alkanolammonium salts are preferred.
• polycarboxylate builders include a variety of categories of useful materials.
• One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, 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. See also "TMS/TDS" builders of 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.
• ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid
• various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
• polycarboxylates such as mellitic acid, succinic acid, oxy- disuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1 ,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
• succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
• a particularly preferred compound of this type is dodecenylsuccinie acid.
• succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, 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.
• the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho- phosphate can be used.
• Phosphonate builders such as ethane-1 - hydroxy-1 ,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used, e.
• Chelating Agents The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
• Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N- hydroxyethylethylenediaminetriacetat.es, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5- disulfobenzene.
• EDDS ethylenediamine disuccinate
• [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
• compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co- builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
• MGDA water-soluble methyl glycine diacetic acid
• these chelating agents will generally comprise from about 0.1 % to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions. f. Clay Soil Removal / Anti-redeposition Agents
• compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
• Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
• the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
• Another group of preferred clay soil removal- antiredeposition agents are the cationic compounds disclosed in European Patent Application 111 ,965, Oh and Gosselink, published June 27, 1984.
• Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
• CMC carboxy methyl cellulose
• compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
• dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
• the polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: R-A x - P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
• x is 0 or 1 ;
• R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
• R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
• the N-O group can be represented by the following general structures:
• the amine oxide unit of the polyamine N- oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6. Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
• suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
• the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1 :1 ,000,000.
• the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
• the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000,000; more preferred 1 ,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
• poly(4- vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
• Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also suitable for use herein.
• the PVPVI has an average molecular weight range from 5,000 to 1 ,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113.
• the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1 , more preferably from 0.8:1 to 0.3:1 , most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
• the present invention also may employ as a dye transfer inhibitor a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
• PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696.
• Compositions containing PVP dye transfer inhibitors can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1 ,000 to about 10,000.
• the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1 , and more preferably from about 3:1 to about 10:1.
• Enzymes Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
• Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
• bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
• Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
• Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
• Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.
• Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
• Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning- effective amount".
• cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1% by weight of a commercial enzyme preparation.
• Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
• AU Anson units
• proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
• One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
• proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
• proteases include those of WO 9510591 A to Procter & Gamble .
• a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
• a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
• an especially preferred protease is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
• Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes include, for example, -amylases described in GB 1 ,296,839 to Novo; RAPIDASE®, International Bio- Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
• Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11 , June 1985, pp. 6518-6521.
• Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
• These preferred amylases herein share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11 , measured versus the above-identified reference-point amylase.
• oxidative stability e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10
• thermal stability e.g.
• Stability-enhanced amylases can be obtained from Novo or from Genencor International.
• One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus - amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
• Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
• Such preferred amylases include (a) an amylase according to the hereinbefore referenced WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.
• Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
• Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
• amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
• Specific amylase enzymes for use in the detergent compositions of the present invention include -amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas -amylase activity assay. (Such Phadebas -amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are -amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated into laundry detergent compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.
• Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
• U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
• Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
• CAREZYME® and CELLUZYME® are especially useful. See also WO 9117243 to Novo.
• Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
• lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
• the lipase variant may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
• the present invention provides the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing the AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in the range of about 50 LU to about 8500 LU per liter of wash solution.
• Cutinase enzymes suitable for use herein are described in WO
• Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
• oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
• Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
• Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
• a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
• Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. i. Enzyme Stabilizing Agent
• Enzyme-containing including but not limited to, liquid compositions, herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent- ready enzymes.
• Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
• One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
• Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
• Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated.
• Preferably water- soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
• Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
• Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
• Stabilizing systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
• chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in-use is sometimes problematic.
• Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
• Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
• EDTA ethylenediaminetetracetic acid
• MEA monoethanolamine
• special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility.
• Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
• the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results.
• the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients, if used.
• such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al. j. Fabric Softeners
• SRA polymeric soil release agents
• SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
• Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
• SRA's can include a variety of charged, e.g., anionic or even cationic species, see U.S. 4,956,447, issued September 11 , 1990 to Gosselink, et al., as well as noncharged monomer units, and their structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
• Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
• esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
• Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
• ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligome zation procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
• DMT dimethyl terephthalate
• PG ,2-propylene glycol
• SRA's include the nonionic end-capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
• SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
• Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me- capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
• SRA's also include: simple copolymehc blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
• methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
• Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
• Suitable SRA's characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from DuPont and MILEASE T from ICI. Another preferred SRA is an oligomer having empirical formula
• which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1 ,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy- 1 ,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1 , and two end-cap units derived from sodium 2-(2- hydroxyethoxy)-ethanesulfonate.
• Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
• Suitable monomers for the above SRA include Na-2-(2- hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl-5-sulfo- isophthalate, EG and PG.
• oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2- oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof.
• CAP, EG/PG, PEG, T and SIP are as defined hereinabove
• DEG represents di(oxyethylene)oxy units
• SEG represents units derived from the sulfoethyl ether of glycerin and related moiety units
• B represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone
• x is from about 1 to about 12
• y' is from about 0.5 to about 25
• y" is from 0 to about 12
• y"' is from 0 to about 10
• z is from about 1.5 to about 25
• z' is from 0 to about 12
• q is from about 0.05 to
• SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2- hydroxyethoxy) ethoxy ⁇ ethanesulfonate (“SE3”) and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol.
• Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2-hydroxy- ethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxy- ethoxy)ethoxy ⁇ ethoxy]ethanesulfonate, DMT, sodium 2-(2,3- dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as
• CAP CAP2(T)5(EG/PG)1.4(SEG)2.5(B)0.13
• CAP is (Na+- O3S[CH2CH2O]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.
• Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201 ,824, Violland et al. and U.S.
• Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
• Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti- redeposition.
• Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
• Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
• Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
• the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
• the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 :1 , more preferably from about 10:1 to 2:1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
• Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
• Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1 ,500 to about 10,000.
• Polyaspartate and poiyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
• Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000. m. Suds Suppressors
• compositions of the present invention Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention.
• suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
• One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
• the monocarboxylic fatty acids and salts thereof used 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.
• the detergent compositions herein may also contain non- surfactant suds suppressors.
• non- surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
• suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) 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 50°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 100°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.
• the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
• 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 suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S. Other silicone suds suppressors are disclosed in U.S. Patent
• 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
• silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
• Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
• An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
• the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
• the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
• typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1 , preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
• a primary antifoam agent which is a mixture of (a) a polyorgano
• the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1 ,000, preferably between about 100 and 800.
• the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
• the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1 ,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
• Preferred is a weight ratio of between about 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
• the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
• suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
• the secondary alcohols include the CQ- C-
• a preferred alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12.
• Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
• Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
• suds should not form to the extent that they overflow the washing machine.
• Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
• Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
• the compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
• fatty monocarboxylate suds suppressor is utilized.
• Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
• Preferably from about 0.01 % to about 1 % of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
• these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
• Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1 % to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions. n. Other Ingredients
• compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
• suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
• the C-10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
• Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
• soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
• Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
• the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
• the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
• a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C ⁇ 3.-15 ethoxylated alcohol (EO 7) nonionic surfactant.
• the enzyme/surfactant solution is 2.5 X the weight of silica.
• the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
• silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
• the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
• ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
• Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
• Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3- propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
• the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
• the detergent compositions herein 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 10.5.
• Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0.
• Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Examples
• Example 1 This example shows a granule detergent composition of the present invention.
• Protease Enzyme proteose cleavage activity at 1.0 AU/g
• Amylase Enzyme amlase activity at 60,000 AMU/g
• Lipase Enzyme lipase activity at 100,000 LU/g
• This example shows a liquid detergent composition of the present invention.
• Protease Enzyme proteose cleavage activity at 1.0 AU/g
• Lipase Enzyme lipase activity at 100,000 LU/g
• This example shows a bar detergent composition of the present invention.
• Protease Enzyme (protease activity at 1.0 AU/g) 0.10
• Amylase Enzyme (amylase activity at 60,000 AMU/g) 0.75
• Lipase Enzyme (lipase activity at 100,000 LU/g) 0.1
• Cellulase Enzyme (cellulase activity at 5,000 CEVU/g) 0.15 Water (including water of hydration), sodium sulfate and other minor ingredients) balance
• Example 4 This example shows a method for machine washing fabric using the composition of Example 1.
• White clothes are sorted and washed separately from colored clothes. 40g of the composition of Example 1 is place in the automatic washing machine. White clothes having a total weight of approximately 1.5kg are then added to the washer. After turning on the washer, the washer adds approximately 33 liters of water. The washer is allowed to continue through its automatic cycle of approximately a 10 minute wash followed by two batch rinses. The clothes are then allowed to air, sun or machine dry. The washed clothes have no yellowing and the white clothes retain their whiteness.
• Example 5 Example 5
• This example shows a method for hand washing fabric using the composition of Example 1.
• Example 1 Approximately 10 liters of water is placed in a basin. 40g of the composition of Example 1 is dissolved in the water.
• the white clothes (approximately 1.5 kg) are washed separately from the colored clothes. The clothes are scrubbed between the hands or by scrubbing them against a wash board. The clothes are occasionally dipped into the wash solution during scrubbing. After all the clothes have been washed, the wash solutions is discarded and replaced with fresh clean water for rinsing. Rinsing is done by swirling and scrubbing the clothes together between the hands and squeezing the water out of the clothes. The rinse water is replaced with fresh clean rinse water. Rinsing and replacement of rinse water continues until the last rinse water is clean and without visible and persistent suds. After rinsing, the clothes are either air, sun or machine dried. The washed clothes have no yellowing and the white clothes retain their whiteness.
• Example 6 This example shows a method for cleaning fabric using the composition of Example 2.
• White clothes are pre-rinsed to remove any particulate soils in a basin containing approximately 20 liters of water. The pre-rinse water is discarded and replaced with fresh clean water.
• the clothes are washed one by one by directly applying the bar into the fabric and then scrubbing between the hands, or by using a scrubbing implement such as a scrubbing board. When all the clothes are washed, the wash water is discarded and replaced with fresh clean water.
• the clothes are then batch rinsed until there is no visible sign of suds or until the last rinse water is clear. After rinsing, the clothes are either air, sun or machine dried. The clothes are then allowed to machine dry or air dry. The washed clothes have no yellowing and the white clothes retain their whiteness.
• Example 7 This example shows a method for cleaning fabric using the composition of Example 3. White clothes are washed separately from the colored clothes.
• Stains and soils that are concentrated in a particular area are pretreated with a small amount of the composition of Example 3.
• the clothes (approximately 1.5 kg) are then placed in an automatic washing machine. 39.6 g of the composition of Example 3 is further added to the clothes in the machine. After turning on the washer, the washer adds approximately 33 liters of water. The washer is allowed to continue through its automatic cycle of approximately a 10 minute wash followed by two 3-min rinses). After rinsing, the clothes are either air, sun or machine dried. The clothes are then allowed to machine dry or air dry. The washed clothes have no yellowing and the white clothes retain their whiteness.

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• 1996
  • 1996-10-17 JP JP9536157A patent/JPH11500181A/ja active Pending
  • 1996-10-17 AU AU74643/96A patent/AU7464396A/en not_active Abandoned
  • 1996-10-17 WO PCT/US1996/016651 patent/WO1998016612A1/en active Application Filing
  • 1996-10-17 BR BR9612751-1A patent/BR9612751A/pt unknown
• 1997
  • 1997-10-17 AR ARP970104806A patent/AR010006A1/es unknown

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