WO2001016281A1 - Aqueous liquid detergent compositions comprising a polymeric stabilization system - Google Patents
Aqueous liquid detergent compositions comprising a polymeric stabilization system Download PDFInfo
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- WO2001016281A1 WO2001016281A1 PCT/US2000/023316 US0023316W WO0116281A1 WO 2001016281 A1 WO2001016281 A1 WO 2001016281A1 US 0023316 W US0023316 W US 0023316W WO 0116281 A1 WO0116281 A1 WO 0116281A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
Definitions
- the present invention relates to aqueous liquid detergent compositions and methods of using such compositions to launder fabrics. More specifically, the present invention relates to aqueous liquid detergent compositions comprising one or more particulate solids such as peroxycarboxylic acids (“peracid”) and a polymeric stabilization system.
- peracid peroxycarboxylic acids
- Suspending systems for suspending solid particles in liquid compositions have been employed in specific types of cleaning and personal care compositions in the past.
- suspending systems comprising surfactant phases and/or surfactant structuring liquids have been incorporated into liquid detergent compositions.
- surfactant-based suspending systems examples include EP 442 549 B 1 , US 4,828,747, EP 160 342 B2, EP 386 566 Al , US 5,391,324, EP 668 903 and 5,409,632, which all deal with the suspension of preformed poorly water soluble peracids using surfactant phases.
- surfactant phases are made using (i) one or more nonionic surfactants (low electrolyte) or (ii) combinations of anionic and/or nonionic surfactants with fatty acids and/or electrolytes.
- GB 2279660 describes the use of xanthan gum as a suspending agent for solid particles in a liquid detergent product. More specifically, GB 2279660 discloses a stable, pourable aqueous liquid laundry detergent composition comprising xanthan gum (a polysaccharide polymer) for phase stability, along with a specific pH jump system for cleaning performance and product bleach stability, in a peroxyacid-containing suspension. This is accomplished without the use of a stability enhancing polymer which is a copolymer of a hydrophobic and a hydrophilic monomer.
- U.S. Patent No. 4,879,057 to Dankowski et al discloses aqueous bleaching suspensions including peroxycarboxylic acid suspended in a carrier liquid in the presence of an organic thickening agent and of an acidifying agent.
- the suspensions contain agar or xanthan polysaccharide as a thickening agent, and a hydrate-forming neutral salt.
- aqueous liquid laundry detergent products which contain suspended solids such as solid, substantially water-insoluble peroxyacid can have phase stability problems, particulary across the varying environmental temperatures to which such products may be exposed.
- product detergent surfactant levels are increased in such compositions for better cleaning and bleaching performance, product viscosity often increases to unacceptable levels.
- polymeric stabilization systems of the present invention especially ethoxylated polymers and/or low levels ( ⁇ 1%) of ethoxylated nonionics in aqueous liquid detergent compositions to stabilize solid particles, such as substantially water-insoluble peroxycarboxylic acids and/or to reduce eye irritation of the compositions is not known, nor has it been suggested in the prior art.
- an aqueous liquid detergent composition comprising one or more particulate solids such as peroxycarboxylic acids (“peracid”) and a polymeric stabilization system, and a method for laundering fabrics using such a composition.
- peracid peroxycarboxylic acids
- the present invention meets and fulfills the needs identified above by providing an aqueous liquid detergent composition comprising one or more particulate solids such as peroxycarboxylic acids (“peracid”) and a polymeric stabilization system.
- aqueous liquid detergent composition comprising one or more particulate solids such as peroxycarboxylic acids (“peracid”) and a polymeric stabilization system.
- R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group
- Y is hydrogen, halogen, alkyl, aryl, - C(0)OH or -C(0)OOH.
- polymeric compounds for use in the compositions of the present invention include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, polyvinyl acetate polymers and mixtures thereof, examples of which are described in U.S. Patent No. 5,817,614 to Miracle et al. If used, these polymeric compounds 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%.
- Polymeric polycarboxylate materials can also be used as polymeric compounds in accordance with the present invention.
- Such 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.
- 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 Dec. 15, 1982, as well as in EP 193,360, published Sep. 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
- Still other useful polymeric compounds from this class 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 compound which can be included is polyethylene glycol (PEG).
- Gosselink for example produced from DMT, 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.
- Another preferred polymeric compound is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP) ⁇ 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-l,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.
- CAP empirical formula
- 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.
- Preferred of such esters are those of empirical formula:
- 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 homologues and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol.
- Preferred polymeric compound esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2-hydroxyethoxy)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)2(T)5(EG/PG)1 4(SEG)2.5(B)0.13 wherein CAP is (Na+ - ⁇ 3S[CH2CH2 ⁇ ]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.
- Still yet another preferred class of polymeric compounds for use in the vompositions of the present invention include oligomeric, substantially linear, sulfonated poly-ethoxy/propoxy end-capped esters, examples of which and methods of preparation are described in U S. Patent No. 5,415,807 to Gosselink et al.
- the esters comprise oxyethyleneoxy units and terephthaloyl units.
- Preferred esters additionally comprise units of oxy-l ,2-propyleneoxy, sulfoisophthalate and, optionally, poly(oxyethylene)oxy units (with degee of polymerization from 2 to 4).
- the esters are of relatively low molecular weight, typically ranging from about 500 to about 8,000.
- the polymeric compounds of this class encompass an oligomeric ester "backbone" which is end-capped on one, or preferably both, ends of the backbone by the essential end-capping units.
- the essential end-capping units are anionic hydrophiles de ⁇ ved from sulfonated poly- ethoxy/propoxy groups and connected to the esters by an ester linkage.
- the preferred end-capping units are of the formula (MO.sub.3 S)(CH.sub.2).sub.m (CH.sub.2 CH.sub.2 0)(RO).sub.n ⁇ wherein N is a salt- forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene, or a mixture thereof, and n is from 0 to 2; and mixtures thereof.
- the polymeric compounds for use in the compositions of the present invention are the polymeric compounds described in U.S. Patent No. 4,968,451 to Scheibel et al.
- cleaning adjunct materials include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, fabric softening agents, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, processing aids, pigments and pH control agents as described in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and
- cleaning adjunct materials are not compatible with the other ingredients present in the aqueous liquid detergent compositions of the present invention, then suitable methods of keeping the incompatible cleaning adjunct materials and the other ingredients separate (not in contact with each other) until combination of the two components is appropriate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc.
- the aqueous liquid detergent compositions may include from about 1% to about 99.9% by weight of the composition of the cleaning adjunct materials.
- fabric laundry compositions include hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics.
- the compositions of the present invention preferably contain both a surfactant and a builder compound and additionally one or more cleaning adjunct materials preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
- Laundry compositions can also contain softening agents, as additional cleaning adjunct materials.
- aqueous liquid detergent compositions of the present invention can also be used as detergent additive products in liquid form.
- Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the laundry process.
- the aqueous liquid detergent compositions according to the present invention can be in a "concentrated form", in such case, the aqueous liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
- the water content of the concentrated aqueous liquid detergent composition is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the composition.
- aqueous liquid detergent compositions according to the present invention may be isotropic liquids, aqueous gels and colored liquid compositions.
- the aqueous liquid detergent compositions of the present invention preferably comprise a surfactant system which preferably contains one or more detersive co-surfactants.
- the co- surfactants can be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, biodegradably branched surfactants and mixtures thereof.
- the surfactant system typically comprises from about 5% to about 70%, preferably from about 15% to about 30%, by weight of the detergent composition. i. Anionic Surfactant
- Anionic surfactants include Cj i-Ci g alkyl benzene sulfonates (LAS) and primary, branched-chain and random C ] Q-C20 alkyl sulfates (AS), the Cjo-Cj g secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOS0 3 " M + ) CH 3 and CH 3 (CH 2 ) y (CHOS0 3 " M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the CI Q- C j g alkyl alkoxy sulfates ("AE X S"; especially EO 1 -7 ethoxy sulfates), Ci Q -Ci g alkyl alkoxy carboxylates (especially the
- anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841 , Barrat et al, issued August 25, 1981, and in U.S. Patent No. 3,919,678, Laughlin et al, issued December 30, 1975.
- Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of aryl groups.
- Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-
- Ci g carbon atoms such as those produced by reducing the glycerides of tallow or coconut oil.
- anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
- Other useful anionic surfactants herein include the water-soluble salts of esters of a- sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- Particularly preferred anionic surfactants herein are the alkyl sulfates, in particular, the alkyl polyethoxylate sulfates of the formula:
- the fatty acids useful in the present invention as anionic surfactants include saturated and/or unsaturated fatty acids obtained from natural sources or synthetically prepared.
- suitable fatty acids include, but are not limited to, capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid.
- Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
- Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678,
- exemplary, non-limiting classes of useful nonionic surfactants include: Cg-C j g alkyl ethoxylates ("AE"), with EO about 1-22, including the so-called narrow peaked alkyl ethoxylates and Cg-Ci 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), alkyl dialkyl amine oxide, alkanoyl glucose amide, and mixtures thereof.
- AE alkyl ethoxylates
- compositions of the present invention will preferably contain up to about 10%, preferably from 0% to about 5%, more preferably from 0% to about 3%, by weight of an nonionic surfactant.
- an nonionic surfactant Preferred are the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
- R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
- ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol.
- nonionic surfactants for use herein include, but are not limited to: The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols.
- the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
- the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
- nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Corporation; and Triton® X-45, X-l 14, X-100, and X-102, all marketed by the Rohm & Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
- alkyl phenol alkoxylates e.g., alkyl phenol ethoxylates.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
- nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as "alkyl ethoxylates.”
- the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
- the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
- Examples of compounds of this type include certain of the commercially-available Pluronic® surfactants, marketed by BASF.
- the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
- This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1,000.
- this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF.
- Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
- Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
- R ⁇ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms;
- R" is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof;
- x is from 0 to about 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
- the R- > groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
- amine oxide surfactants in particular include C ⁇ Q-C ⁇ g alkyl dimethyl amine oxides and C -Cj2 alkoxy ethyl dihydroxy ethyl amine oxides.
- Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
- the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
- the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
- the preferred alkyleneoxide is ethylene oxide.
- Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
- the alkyl group is a straight chain saturated alkyl group.
- the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
- Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, terra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
- Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
- the preferred alkylpolyglycosides have the formula
- R2 ⁇ (C n H 2n O) t (glycosyl) x wherein R ⁇ is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
- the glycosyl is preferably derived from glucose.
- the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
- the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
- Fatty acid amide surfactants having the formula:
- R ⁇ is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R' is selected from the group consisting of hydrogen, C j -C4 alkyl, C1-C4 hydroxyalkyl, and -(C ⁇ H4 ⁇ ) x H where x varies from about 1 to about 3.
- Preferred amides are Cg-C20 ammonia amides, monoethanolamides, dietha-nolamides, and isopropanolamides.
- Conventional nonionic and amphoteric surfactants include C ⁇ -C j g alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and Cg-C j 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy).
- AE alkyl ethoxylates
- Cg-C j 2 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
- the Ci -C ⁇ g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -C j g N- methylglucamides. See WO 9,206,154.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C] Q-C] g N-(3-methoxypropyl) glucamide.
- the N-propyl through N-hexyl C ⁇ -Cj glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C j o-C j g soaps may be used.
- nonionic surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued
- these surfactants include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
- R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
- ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful.
- the structure (I) provides one long-chain moiety R! (EO) X (PO) V (BO) Z and two short chain moieties, CH2R'.
- R' is preferably selected from hydrogen, methyl and -CH2OH.
- R is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R s a primary alkyl moiety.
- R! is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
- R! may be somewhat longer, having a chainlength in the range C12-C24.
- Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
- Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
- Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
- Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof.
- R' is H
- R' is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
- the present invention includes important embodiments comprising at least one biodegradably branched and/or crystallinity disrupted and/or mid-chain branched surfactant or surfactant mixture.
- biodegradably branched and/or crystallinity disrupted and/or mid-chain branched indicate that such surfactants or surfactant mixtures are characterized by the presence of surfactant molecules having a moderately non-linear hydrophobe; more particularly, wherein the surfactant hydrophobe is not completely linear, on one hand, nor is it branched to an extent that would result in unacceptable biodegradation.
- the preferred biodegradably branched surfactants are distinct from the known commercial LAS, ABS, Exxal, Lial, etc. types, whether branched or unbranched.
- the biodegradably branched materials comprise particularly positioned light branching, for example from about one to about three methyl, and/or ethyl, and/or propyl or and/or butyl branches in the hydrophobe, wherein the branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe.
- branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe.
- Typically from one to three such branches can be present on a single hydrophobe, preferably only one.
- Such biodegradably branched surfactants can have exclusively linear aliphatic hydrophobes, or the hydrophobes can include cycloaliphatic or aromatic substitution.
- MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and linear alkylbenzenesulfonate surfactants said surfactant suitably being selected from mid-chain-C,-C 4 -branched C 8 -C, 8 -alkyl sulfates, mid-chain-C,-C 4 -branched C 8 -C 18 - alkyl ethoxylated, propoxylated or butoxylated alcohols, mid-chain-C,-C 4 -branched C 8 -C 18 -alkyl ethoxysulfates, mid-chain-C,-C 4 -branched C 8 -C, 6 -alkyl benzenesulfonates and mixtures thereof.
- the surfactants can in general be in acid or salt, for example sodium, potassium, ammonium or substituted ammonium, form.
- the biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization.
- Such surfactants can, in general, belong to any known class of surfactants, e.g., anionic, nonionic, cationic, or zwitterionic.
- the biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol.
- MCB nonionic surfactants including MCB primary alkyl polyoxyalkylenes of formula (1):
- Such MCB nonionics can alternately include butylene oxide derived moieties, and the -OH moiety can be replaced by any of the well-known end-capping moieties used for conventional nonionic surfactants.
- W097/38957 A also discloses (i) production of MCB alkyl sulphate surfactants by sulphating (I) or (II); (ii) preparation of MCB alkylethoxy sulphates which comprises ethoxylating and then sulphating (I) or (II); (iii) preparation of MCB alkyl carboxylate surfactants which comprises oxidising (I) or (II) or their aldehyde intermediates and (iv) preparation of MCB acyl taurate, MCB acyl isethionate, MCB acyl sarcosinate or MCB acyl N- methylglucamide surfactants using the branched alkyl carboxylates as feedstock.
- W097/38956 A published 10/23/97 discloses the preparation of mid- to near mid-chain branched alpha olefins which is effected by: (a) preparing a mixture of carbon monoxide and hydrogen; (b) reacting this mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a hydrocarbon mixture comprising the described olefins; and (c) separating the olefins from the hydrocarbon mixture.
- W097/38956 A further discloses the preparation of mid- to near mid-chain branched alcohols by reacting the olefins described with CO/H 2 under Oxo conditions.
- These alcohols can be used to prepare (1) MCB sulphate surfactants by sulphating the alcohols; (2) MCB alkyl ethoxy sulphates by ethoxylating, then sulphating, the alcohols; or (3) branched alkyl carboxylate surfactants by oxidising the alcohols or their aldehyde intermediates.
- the branched carboxylates formed can be used as a feedstock to prepare branched acyl taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide surfactants, etc.
- WO97/39091 A published 10/23/97 includes disclosure of a detergent surfactant composition comprising at least 0.5 (especially 5, more especially 10, most especially 20) wt% of longer alkyl chain, MCB surfactant of formula (I).
- WO97/39089 A published 10/23/97 includes disclosure of liquid cleaning compositions comprising: (a) as part of surfactant system 0.1-50 (especially 1-40) wt % of a mid-chain branched surfactant of formula (I); (b) as the other part of the surfactant system 0.1-50 wt% of co- surfactant(s); (c) 1-99.7 wt% of a solvent; and (d) 0.1-75 wt% of adjunct ingredients.
- WO97/39088 A also discloses (1) a surfactant composition comprising a mixture of branched primary alkyl sulphates of formula (I) as above.
- M is a water-soluble cation;
- a detergent composition comprising: (a) 0.001 -99% of MCB primary alkyl alkoxylated sulphate of formula (III) and/or (IV):
- WO97/39087 A published 10/23/97 includes disclosure of a surfactant composition
- the alkyl alkoxylated sulphates may be produced directly from the polyoxyalkylene alcohol by sulphating with S0 3 and neutralising.
- WO 98/23566 A Shell, published 06/04/98 discloses branched primary alcohol compositions having 8-36 C atoms and an average number of branches per mol of 0.7-3 and comprising ethyl and methyl branches. Also disclosed are: (1) a branched primary alkoxylate composition preparable by reacting a branched primary alcohol composition as above with an oxirane compound; (2) a branched primary alcohol sulphate preparable by sulphating a primary alcohol composition as above; (3) a branched alkoxylated primary alcohol sulphate preparable by alkoxylating and sulphating a branched alcohol composition as above; (4) a branched primary alcohol carboxylate preparable by oxidising a branched primary alcohol composition as above; (5) a detergent composition comprising: (a) surfactant(s) selected from branched primary alcohol alkoxylates as in (1), branched primary alcohol sulphates as in (2), and branched alkoxylated primary
- Biodegradably branched surfactants useful herein also include the modified alkylaromatic, especially modified alkylbenzenesulfonate surfactants described in copending commonly assigned patent applications (P&G Case Nos. 7303P, 7304P).
- these surfactants include (P&G Case 6766P) alkylarylsulfonate surfactant systems comprising from about 10% to about 100% by weight of said surfactant system of two or more crystallinity- disrupted alkylarylsulfonate surfactants of formula (B-Ar-D) a (Ml + )b wherein D is SO3 " , M is a cation or cation mixture, q is the valence of said cation, a and b are numbers selected such that said composition is electroneutral; Ar is selected from benzene, toluene, and combinations thereof; and B comprises the sum of at least one primary hydrocarbyl moiety containing from 5 to 20 carbon atoms and one or more
- compositions also include surfactant mixtures comprising (preferably, consisting essentially of): (a) from about 60% to about 95% by weight (preferably from about 65% to about 90%, more preferably from about 70% to about 85%) of a mixture of branched alkylbenzenesulfonates having fo
- L is an acyclic aliphatic moiety consisting of carbon and hydrogen and having two methyl termini
- said mixture of branched alkylbenzenesulfonates contains two or more (preferably at least three, optionally more) of said compounds differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzenesulfonates is characterized by an average carbon content of from about 10.0 to about 14.0 carbon atoms (preferably from about 1 1.0 to about 13.0, more preferably from about 1 1.5 to about 12.5), wherein said average carbon content is based on the sum of carbon atoms in R', L and R 2 , (preferably said sum of carbon atoms in R', L and R 2 is from 9 to 15, more preferably, 10 to 14) and further, wherein L has no substituents other than A, R 1 and R 2 ; M is a cation or cation mixture (preferably selected from H, Na, K, Ca, M
- Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein Y has an average carbon content of from about 10.0 to about 14.0 (preferably from about 1 1.0 to about
- composition is further characterized by a 2/3-phenyl index of from about 350 to about 10,000 (preferably from about 400 to about 1200, more preferably from about 500 to about 700) (and also preferably wherein said surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, more preferably still, from 0 to 0.05).
- surfactant mixtures comprising the product of a process comprising the steps of: alkylating benzene with an alkylating mixture; sulfonating the product of (I); and neutralizing the product of (II); wherein said alkylating mixture comprises: (a) from about 1% to about 99.9%, by weight of branched C 7 -C 20 monoolefins, said branched monoolefins having structures identical with those of the branched monoolefins formed by dehydrogenating branched parafins of formula
- R'LR 2 wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls; R 1 is C, to C 3 alkyl; and R 2 is selected from H and C, to C 3 alkyl; and (b) from about 0.1% to about 85%, by weight of C 7 -C 20 linear aliphatic olefins; wherein said alkylating mixture contains said branched C 7 -C 20 monoolefins having at least two different carbon numbers in said C 7 -C 20 range, and has a mean carbon content of from about 9.5 to about 14.5 carbon atoms; and wherein said components (a) and (b) are at a weight ratio of at least about
- Ampholytic Surfactant - Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
- One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S.
- Preferred amphoteric include C j 2 -Ci g alkyl ethoxylates
- AE alkyl ethoxylate
- Cg-C ⁇ lkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
- Ci 2-C ⁇ g betaines and sulfobetaines sultaines
- C J Q-C I g amine oxides and mixtures thereof.
- Rl is H, C1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C ] -C4 alkyl, more preferably Cj or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C j 1 -C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
- Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
- high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
- Z preferably will be selected from the group consisting of -CH2- (CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n . j -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR)(CHOH)- CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
- R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
- R2-CO-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-deoxymaltotriotityl, etc.
- Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula (i): R ] R2R3R4N + X" wherein R ] is C -C j 6 alkyl, each of R2, R3 and R4 is independently C1 -C4 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4Q) X H where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
- the preferred alkyl chain length for R j is C j 2- C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
- Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulfate, acetate and phosphate ions.
- Suitable quaternary ammonium compounds of formulae (i) for use herein are include, but are not limited to: coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C ⁇ 2-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R j is CH2-CH2-0-C-CJ2-14 alkyl and R2R3R4 are methyl);
- compositions of the present invention typically comprise from about 0.2%, preferably from about 1% to about 25%, preferably to about 8% by weight of such cationic surfactants.
- Zwitterionic Surfactant - Zwitterionic surfactants examples of which are described in U.S. Patent No. 3,929,678, are also suitable for use in the compositions of the present invention.
- compositions of the present invention typically comprise from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such zwitterionic surfactants.
- Diamine Surfactant A particularly preferred class of surfactants for use in liquid dishwashing compositions of the present invention are diamines.
- composition of the present invention may and preferably do comprise a suspending agent.
- a suspending agent is an ingredient which is specifically added to the composition of the present invention to suspend a particulate solid ingredient of the composition.
- suspending agents are those known in the art.
- suspending agents include gum-type polymers (e.g. xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof and polycarboxylate polymers including, but not limited to, : tamarind gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other industrial gums and polymers, which include, but are not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seed, quince seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan, chitin, hydroxyalkyl cellulose, arabinan (preferably from sugar beets), de-branched arabinan (preferably from sugar beets), arabinoxylan (preferably from rye and wheat
- the suspending agent is selected from a gum-type polymer or a polycarboxylate polymer.
- the gum-type polymer when present, is preferably present at a level of from 0.01% to 10%, most preferably from 0.1% to 3%.
- the suspending agent comprises a combination of at least two polymers.
- the first polymer is a gum-type polymer and the second is a cross-linked polycarboxylate polymer.
- the composition may additionally comprise further polymers.
- the ratio of gum-type polymer to cross-linked polycarboxylate polymer is from 100:1 to 1 : 100, most preferably from 1 : 10 to 10: 1.
- aqueous liquid detergent compositions of the present invention as described hereinbefore may optionally include, in addition to the particulate solid(s), polymeric stabilization system and preferably one or more of the preferred cleaning adjunct materials discussed above, one or more optional cleaning adjunct materials described below.
- the aqueous liquid detergent compositions of the present invention may comprise a bleaching system, in addition to the preformed peracid compound described hereinabove.
- Bleaching systems typically comprise a "bleaching agent” (source of hydrogen peroxide) and an "initiator” or “catalyst".
- bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition.
- the amount of bleach activator will typically be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition comprising the bleaching agent-plus-bleach activator.
- Bleaching Agents Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.
- the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
- perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
- sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
- Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources 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% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
- the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
- Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
- compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material.
- a chlorine-type bleaching material such agents are well known in the art, and include for example sodium dichloroisocyanurate (“NaDCC").
- NaDCC sodium dichloroisocyanurate
- chlorine-type bleaches are less preferred for compositions which comprise enzymes.
- the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
- the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
- Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C J Q-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
- Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
- Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) amino hexanoyloxyj-benzene sulfonate sodium salt (NACA-OBS) an example of which is described in U.S. Patent No. 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate
- NOBS nonanoyloxybenzenesulphonate
- NACA-OBS 4-[N-(nonaoyl) amino hexanoyloxyj-benzene sulfonate sodium salt
- LOBS or C12-OBS dodecanoyloxybenzenesulphonate
- Preferred bleach activators are those described in U.S. 5,698,504 Christie et al., issued December 16, 1997; U.S. 5,695,679 Christie et al. issued December 9, 1997; U.S. 5,686,401 Willey et al., issued November 1 1, 1997; U.S. 5,686,014 Hartshorn et al, issued November 11, 1997; U.S. 5,405,412 Willey et al., issued April 1 1, 1995; U.S. 5,405,413 Willey et al., issued April 11, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S. 4,412,934 Chung et al., issued November 1, 1983, and copending patent applications U. S. Serial Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference.
- the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1, preferably from about 20: 1, more preferably from about 10:1 to about 1 : 1, preferably to about 3:1.
- Quaternary substituted bleach activators may also be included.
- the present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
- QSBA quaternary substituted bleach activator
- QSP quaternary substituted peracid
- Preferred QSBA structures are further described in U.S. 5,686,015 Willey et al., issued November 1 1 , 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselink et al, issued October 24, 1995; U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al., issued November 26, 1996; all of which are incorporated herein by reference.
- bleach activators useful herein are amide-substituted as described in U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above.
- Preferred examples of such bleach activators include: (6-octanamido- caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate and mixtures thereof.
- compositions and methods may utilize metal-containing bleach catalysts that are effective for use in bleaching compositions.
- metal-containing bleach catalysts that are effective for use in bleaching compositions.
- Preferred are manganese and cobalt-containing bleach catalysts.
- compositions herein can be catalyzed by means of a manganese compound.
- a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621 ; 5,244,594; 5,194,416; and 5,1 14,606; and European Pat. App. Pub. Nos.
- Preferred examples of these catalysts include Mn IV 2(u-0) 3 ( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(PF 6 ) 2 , Mn m 2(u-0) ⁇ (u-OAc) ( 1 ,4,7- trimethyl- 1 ,4,7-triazacyclononane)2(Cl ⁇ 4)2, Mn 1 ⁇ 4(u-0)g( 1 ,4,7-triazacyclononane)4(C104)4, Mn ⁇ Mn IV 4(u-0) j (u-OAc) .( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane) 2 (Cl ⁇ 4)3 , Mn IV ( 1 ,4,7- trimethyl- 1 ,4, 7-triazacyclononane)- (OC ⁇ PFg), and mixtures
- cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] Ty, wherein "OAc” represents an acetate moiety and "T y " is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]Cl2; as well as
- Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand.
- the phrase "macropolycyclic rigid ligand” is sometimes abbreviated as "MRL” in discussion below.
- the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb” denotes parts per billion by weight and "ppm” denotes parts per million by weight).
- "rigid” as used herein means that the MRL must be determinably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacking a superstructure (especially linking moieties or, preferably cross-bridging moieties) found in the MRL's.
- parent macrocycle which is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacking a superstructure (especially linking moieties or, preferably cross-bridging moieties) found in the MRL's.
- the practitioner will use the free form (not the metal-bound form) of the macrocycles.
- Rigidity is well-known to be useful in comparing macrocycles; suitable tools for determining, measuring or comparing rigidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta. (1989). 164, 73-84.
- Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV).
- Preferred transition-metals in the instant transition- metal bleach catalyst include manganese, iron and chromium.
- the MRL's (and the corresponding transition-metal catalysts) herein suitably comprise:
- a covalently connected non-metal superstructure capable of increasing the rigidity of the macrocycle, preferably selected from
- a bridging superstructure such as a linking moiety
- a cross-bridging superstructure such as a cross-bridging linking moiety
- Preferred superstructures herein not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft.
- Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used.
- n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or
- Fig. 2 wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like.
- the aromatic ring in 1.10 can be replaced by a saturated ring, in which the atom in Z connecting into the ring can contain N, O, S or C.
- Suitable MRL's are further nonlimitingly illustrated by the following compound:
- this ligand is named 5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1.
- Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and non-limitingly illustrated by any of the following:
- Hexafluorophosphate D ⁇ chloro-5,12-d ⁇ -n-butyl-l ,5,8,12-tetraaza b ⁇ cyclo[6 6 2]hexadecaneManganese(II) D ⁇ chloro-5,12-d ⁇ benzyl-l,5,8,12-tetraazab ⁇ cyclo[6 6 2]hexadecaneManganese(II) D ⁇ chloro-5-n-butyl- 12-methyl- 1,5,8,12-tetraaza-b ⁇ cyclo[6 6 2]hexadecane
- compositions and laundry processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species m the aqueous washing medium, and will preferably provide from about 0 01 ppm to about 25 ppm, more preferably from about 0 05 ppm to about 10 ppm, and most preferably from about 0 1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor
- typical compositions herein will comprise from about 0 0005% to about 0 2%, more preferably from about 0 004%) to about 0 08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions
- Detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits
- Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, hpases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgmnases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases, mannanases, xyloglucanases or mixtures thereof
- a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, hpase, cutinase, mannanases, xyloglucanases and/or cellulase.
- Enzymes when present in the
- Proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-type proteases.
- Preferred for use herein are subtilisin-type proteolytic enzymes.
- Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
- protease D 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 WO 95/10615 published April 20, 1995 by Genencor International (A.
- Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1 , 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101 , 102, 104, 106, 107, 109, 1 1 1, 114, 1 16, 1 17, 119, 121, 123, 126, 128, 130, 131 , 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160
- proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in W091/02792 and their variants described in WO 95/23221.
- protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
- Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
- a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
- a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
- Other suitable proteases are described in EP 516 200 by Unilever.
- proteases useful in the present invention are known as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KAN ASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
- Protease enzymes may be incorporated into the compositions in accordance with the present invention at a level of from about 0.0001% to about 2% active enzyme by weight of the composition.
- enzymes and their directly linked inhibitors e.g., protease and its inhibitor linked by a peptide chain as described in WO 98/13483 A
- enzymes and their non-linked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
- the preferred enzymes herein can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
- Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
- WO94/02597 describes laundry compositions which incorporate mutant amylases. See also WO95/10603.
- Other amylases known for use in laundry compositions include both ⁇ - and ⁇ - amylases.
- ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo).
- amylases are stability-enhanced amylases described in W094/18314 and WO96/05295, Genencor, and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603. Also suitable are amylases described in EP 277 216.
- ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
- W095/26397 describes other suitable amylases : ⁇ -amylases characterised 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. Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.
- compositions of the present invention may also comprise a mannanase enzyme.
- the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1.78 : Endo-l,4- ⁇ -mannosidase, referred therein after as "mannanase” and EC 3.2.1.100 : 1,4- ⁇ -mannobiosidase and mixtures thereof.
- mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1.78 : Endo-l,4- ⁇ -mannosidase, referred therein after as "mannanase” and EC 3.2.1.100 : 1,4- ⁇ -mannobiosidase and mixtures thereof.
- compositions of the present invention when a mannanase is present, comprise a ⁇ -l,4-Mannosidase (E.C. 3.2.1.78) referred to as Mannanase.
- Mannanase or "galactomannanase” denotes a mannanase enzyme defined according to the art as officially being named mannan endo-l,4-beta-mannosidase and having the alternative names beta- mannanase and endo-l,4-mannanase and catalysing the reaction: random hydrolysis of 1,4-beta- D- mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans.
- the oligomers which are released from the mannanases or by a combination of mannanases and ⁇ - galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by ⁇ - mannosidase and/or ⁇ -glucosidase.
- the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source.
- the laundry detergent composition of the present invention will comprise an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12.
- Most preferred mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme originating from Bacillus sp. 1633 as described in the co-pending Danish patent application No. PA 1998 01340.
- alkaline mannanase enzyme is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
- the alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is described in the co-pending U.S. patent application serial No. 09/1 11 ,256.
- this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions 32-343 of SEQ ID NO:2 as shown in U.S. patent application serial No. 09/111,256; or iii) an analogue of the polypeptide defined in i) or ii) which is at least 70% homologous with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:
- polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patent application serial No. 09/1 1 1,256;
- polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 as shown in U.S. patent application serial No. 09/1 1 1,256;
- the plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180.
- a second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is described in the co-pending U.S. patent application serial No. 09/095,163. More specifically, this mannanase is: i) is encoded by the coding part of the DNA sequence shown in SED ID No. 5 shown in the U.S. patent application serial No. 09/095,163 or an analogue of said sequence; and/or ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown in the U.S. patent application serial No.
- polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 the Danish application No. PA 1998 01340;
- a fourth more preferred mannanase is described in the Danish co-pending patent application No. PA 1998 01341. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI 12; ii) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ ID NO:2as shown in the Danish application No. PA 1998 01341; or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of
- compositions of the present invention may also comprise a xyloglucanase enzyme.
- Suitable xyloglucanases for the purpose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition.
- the term "endoglucanase activity” means the capability of the enzyme to hydrolyze 1,4- ⁇ -D-glycosidic linkages present in any cellulosic material, such as cellulose, cellulose derivatives, lichenin, ⁇ -D-glucan, or xyloglucan.
- the endoglucanase activity may be determined in accordance with methods known in the art, examples of which are described in WO 94/14953 and hereinafter.
- One unit of endoglucanase activity e.g. CMCU, AVIU, XGU or BGU
- CMCU CMC
- AVIU acid swollen Avicell
- XGU xyloglucan
- BGU cereal ⁇ -glucan
- the reducing sugars are determined as described in WO 94/14953 and hereinafter.
- the specific activity of an endoglucanase towards a substrate is defined as units/mg of protein.
- SEQ ID NO: 18 or a sequence homologous thereto encoding a polypeptide specific for xyloglucan with endoglucanase activity, ii) is immunologically reactive with an antibody raised against a highly purified endoglucanase encoded by the DNA sequence defined in i) and derived from Aspergillus aculeatus, CBS 101.43, and is specific for xyloglucan.
- the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% with any of the sequences shown above.
- Endoglucanase specific for xyloglucan may be obtained from the fungal species A aculeatus, as described m WO 94/14953 Microbial endoglucanases specific for xyloglucan has also been described in WO 94/14953 Endoglucanases specific for xyloglucan from plants have been described, but these enzymes have transferase activity and therefore must be considered inferior to microbial endoglucanses specific for xyloglucan whenever extensive degradation of xyloglucan is desirable
- An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts in a microbial host, than enzymes of other origins
- the xyloglucanase when present, is incorporated into the compositions of the invention preferably at a level of from 0 0001% to 2%, more preferably from 0 0005% to 0 1%, most preferred from 0 001% to 0 02% pure enzyme by weight of the composition
- the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast o ⁇ gin Origin can further be mesophihc or extremophilic (psychrophihc, psychrotrophic, thermophilic, barophihc, alkalophihc, acidophihc, halophihc, etc ) Purified or non-purified forms of these enzymes may be used nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineering techniques in order to optimize their performance efficiency in the laundry detergent and/or fabric care compositions of the mvention For example, the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased Alternatively, the variant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular laundry application
- SKS-6 is a highly preferred layered silicate for use in the compositions described herein herein, but other such layered silicates, such as those having the general formula NaMSi ⁇ ⁇ 2 x + ⁇ -y ⁇ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably
- the aluminosilicate builder is an aluminosilicate zeolite having the unit cell formula:
- PEG polyethylene glycol
- 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.
- soil release agents include the METOLOSE SMI 00, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
- 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 SRA to be more easily cleaned in later washing procedures.
- compositions of the present invention herein may also optionally contain a chelating agent which serves to chelate metal ions and metal impurities which would otherwise tend to deactivate the bleaching agent(s).
- a chelating agent which serves to chelate metal ions and metal impurities which would otherwise tend to deactivate the bleaching agent(s).
- Useful chelating agents can include any of those known to those skilled in the art such as amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are described in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.
- chelating agents contribute to further enhance the chemical stability of the compositions.
- a chelating agent may be also desired in the compositions of the present invention as it allows to increase the ionic strength of the compositions herein and thus their stain removal and bleaching performance on various surfaces.
- Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1- hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
- the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
- Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1 -hydroxy diphosphonate (HEDP).
- DTPMP diethylene triamine penta methylene phosphonate
- HEDP ethane 1 -hydroxy diphosphonate
- Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
- Polyfunctionally-substituted aromatic chelating agents may also be 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.
- a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
- Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
- Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
- Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
- PDTA propylene diamine tetracetic acid
- MGDA methyl glycine di-acetic acid
- carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
- R j , R 2 , R3, and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -N0 2 , -C(0)R', and -S0 2 R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R5, Rg, R7, and Rg are independently selected from the group consisting of -H and alkyl.
- Suitable radical scavengers for use herein include the well-known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
- Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, l,l,3-tris(2-methyl-4-hydroxy-5-t- butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene.
- Such radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade
- Radical scavengers when used are typically present herein in amounts up to about 10% by weight of the total composition and preferably from about 0.001% to about 0.5% by weight.
- radical scavengers may contribute to the chemical stability of the bleaching compositions of the present invention as well as to the safety profile of the compositions of the present invention.
- suds boosting agents such as Cj Q -C j g alkanolamides can be incorporated into the compositions, typically at about 1 %-10% levels.
- the C ] Q -C ] 4 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 MgCl 2 ,
- suds boosting agents are described in WO 99/27058 and WO 99/27057 both to The Procter & Gamble Company, both published on June 3, 1999. Brighteners
- 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 Tinopal PLC; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[l ,2-d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)- stil- benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
- Biodegradable quaternary ammonium compounds as described in EP-A-040 562 and EP- A-239 910 have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates.
- Non-limiting examples of softener-compatible anions for the quaternary ammonium compounds and amine precursors include chloride or methyl sulfate.
- the detergent compositions of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubihzed and suspended dyes encountered during fabric laundering and conditioning operations involving colored fabrics.
- Additional suitable dye transfer inhibiting agents include, but are not limited to, cross- linked polymers.
- Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
- compositions of the present invention may optionally comprise an effervescent system as described in U.S. Provisional Patent Application Serial Number 60/141 ,340 filed on June 28, 1999 (Attorney Docket "7638P"). pH and Buffering Variation
- Suspending agent can be any of the suspending agents described hereinabove, preferably xanthan gum.
- Example 2 A heavy duty aqueous liquid bleaching composition in a dual compartment bottle is prepared as follows:
- Polymeric stabilization system can be any of the polymeric stabilization systems described hereinabove, preferably its the polymeric stabilization system comprising the polymer described in U.S. Patent No. 4,968,451.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US10/069,627 US6844305B1 (en) | 1999-08-27 | 2000-08-25 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
BR0013652-2A BR0013652A (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
EP00959386A EP1206521A1 (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
AU70720/00A AU7072000A (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
CA002381896A CA2381896A1 (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
MXPA02002130A MXPA02002130A (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system. |
JP2001520829A JP2003508591A (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent composition containing a polymer stabilizing system |
Applications Claiming Priority (2)
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US15123299P | 1999-08-27 | 1999-08-27 | |
US60/151,232 | 1999-08-27 |
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PCT/US2000/023316 WO2001016281A1 (en) | 1999-08-27 | 2000-08-27 | Aqueous liquid detergent compositions comprising a polymeric stabilization system |
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EP (1) | EP1206521A1 (en) |
JP (1) | JP2003508591A (en) |
CN (1) | CN1378589A (en) |
AU (1) | AU7072000A (en) |
BR (1) | BR0013652A (en) |
CA (1) | CA2381896A1 (en) |
MX (1) | MXPA02002130A (en) |
WO (1) | WO2001016281A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1780260A1 (en) * | 2005-10-26 | 2007-05-02 | The Procter & Gamble Company | Process of treating fabrics |
EP3495466A1 (en) * | 2017-12-06 | 2019-06-12 | The Procter & Gamble Company | Use of a liquid laundry detergent composition |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX349259B (en) * | 2011-01-20 | 2017-07-18 | Huntsman Advanced Mat (Switzerland) Gmbh | Formulations of fluorescent whitening agents in dispersed form. |
SG11201604459SA (en) * | 2013-12-06 | 2016-07-28 | Lion Corp | Liquid detergent |
CN104194971B (en) * | 2014-08-25 | 2017-07-18 | 深圳市唯特偶新材料股份有限公司 | A kind of welding fixture microemulsion cleaning agent |
DE102016102485A1 (en) * | 2016-02-12 | 2017-08-17 | Sven Reichwagen | disinfectant |
CN109055041B (en) * | 2018-09-21 | 2021-01-05 | 广州立白企业集团有限公司 | Detergent composition |
JP7138554B2 (en) * | 2018-12-17 | 2022-09-16 | ライオン株式会社 | Liquid detergent composition for textiles |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3944663A (en) * | 1971-06-16 | 1976-03-16 | Colgate Palmolive Company | Mild light duty detergent containing homopolymers of ethylene oxide |
US3996152A (en) * | 1975-03-27 | 1976-12-07 | The Procter & Gamble Company | Bleaching composition |
US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
EP0412599A1 (en) * | 1989-08-08 | 1991-02-13 | Akzo Nobel N.V. | Aqueous peroxide compositions with improved safety profile |
GB2279660A (en) * | 1993-06-30 | 1995-01-11 | Procter & Gamble | Liquid laundry detergents containing alkyl ethoxylate |
US5674828A (en) * | 1996-04-08 | 1997-10-07 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous liquid compositions comprising peracid compounds and defined N-oxide compounds |
WO1997042287A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Liquid detergent compositions comprising specially selected modified polyamine polymers |
WO1997043367A1 (en) * | 1996-05-17 | 1997-11-20 | The Procter & Gamble Company | Detergent composition |
EP1010751A2 (en) * | 1998-12-14 | 2000-06-21 | The Procter & Gamble Company | Bleaching compositions |
-
2000
- 2000-08-27 CA CA002381896A patent/CA2381896A1/en not_active Abandoned
- 2000-08-27 CN CN 00813052 patent/CN1378589A/en active Pending
- 2000-08-27 BR BR0013652-2A patent/BR0013652A/en not_active IP Right Cessation
- 2000-08-27 JP JP2001520829A patent/JP2003508591A/en not_active Withdrawn
- 2000-08-27 AU AU70720/00A patent/AU7072000A/en not_active Abandoned
- 2000-08-27 MX MXPA02002130A patent/MXPA02002130A/en unknown
- 2000-08-27 EP EP00959386A patent/EP1206521A1/en not_active Withdrawn
- 2000-08-27 WO PCT/US2000/023316 patent/WO2001016281A1/en not_active Application Discontinuation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3944663A (en) * | 1971-06-16 | 1976-03-16 | Colgate Palmolive Company | Mild light duty detergent containing homopolymers of ethylene oxide |
US3996152A (en) * | 1975-03-27 | 1976-12-07 | The Procter & Gamble Company | Bleaching composition |
US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
EP0412599A1 (en) * | 1989-08-08 | 1991-02-13 | Akzo Nobel N.V. | Aqueous peroxide compositions with improved safety profile |
GB2279660A (en) * | 1993-06-30 | 1995-01-11 | Procter & Gamble | Liquid laundry detergents containing alkyl ethoxylate |
US5674828A (en) * | 1996-04-08 | 1997-10-07 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous liquid compositions comprising peracid compounds and defined N-oxide compounds |
WO1997042287A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Liquid detergent compositions comprising specially selected modified polyamine polymers |
WO1997043367A1 (en) * | 1996-05-17 | 1997-11-20 | The Procter & Gamble Company | Detergent composition |
EP1010751A2 (en) * | 1998-12-14 | 2000-06-21 | The Procter & Gamble Company | Bleaching compositions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1780260A1 (en) * | 2005-10-26 | 2007-05-02 | The Procter & Gamble Company | Process of treating fabrics |
WO2007049238A1 (en) * | 2005-10-26 | 2007-05-03 | The Procter & Gamble Company | Process of treating fabrics |
EP3495466A1 (en) * | 2017-12-06 | 2019-06-12 | The Procter & Gamble Company | Use of a liquid laundry detergent composition |
Also Published As
Publication number | Publication date |
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MXPA02002130A (en) | 2002-10-17 |
BR0013652A (en) | 2002-05-07 |
JP2003508591A (en) | 2003-03-04 |
CN1378589A (en) | 2002-11-06 |
CA2381896A1 (en) | 2001-03-08 |
EP1206521A1 (en) | 2002-05-22 |
AU7072000A (en) | 2001-03-26 |
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