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WO1998000502A2 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
WO1998000502A2
WO1998000502A2 PCT/US1997/010804 US9710804W WO9800502A2 WO 1998000502 A2 WO1998000502 A2 WO 1998000502A2 US 9710804 W US9710804 W US 9710804W WO 9800502 A2 WO9800502 A2 WO 9800502A2
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WO
WIPO (PCT)
Prior art keywords
detergent composition
composition according
group
alkyl
enzyme
Prior art date
Application number
PCT/US1997/010804
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English (en)
Other versions
WO1998000502A3 (fr
Inventor
Stephen Wayne Heinzman
Peter Robert Foley
Original Assignee
The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of WO1998000502A2 publication Critical patent/WO1998000502A2/fr
Publication of WO1998000502A3 publication Critical patent/WO1998000502A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising an alkoxylated dianionic cleaning agent in combination with an enzyme exhibiting improved cleaning benefits.
  • Most conventional detergent compositions also contain mixtures of various detersive surfactants.
  • various detersive surfactants include various anionic surfactants, especially the alkyl benzene sulfonates and alkyl sulfates and various nonionic surfactants, such as alkyl ethoxy lates and alkylphenol ethoxy lates.
  • Surfactants can be useful in the removal of a wide variety of soils and stains from a variety of surfaces.
  • a problem common to detergent compositions comprising either an enzyme or a surfactant is in- wash soil fragment redeposition. Enzymatic action during the wash removes soils from a soiled substrate surface. It is believed that further in-wash enzymatic action on soils causes said soils to break-up into fragments; it is these fragments that may then redeposit onto the substrate surface.
  • Soil fragment redeposition is believed to be the cause of a variety of problems associated with laundry and dishwashing detergent composition.
  • the off-white appearance of some fabrics can be caused by the redeposition of soil fragments after laundering. Redeposition of soils onto fabrics after laundering may also result in fabric harshness.
  • a problem commonly associated with redeposited soil fragments is the appearance of spot and films on the surface of washed substrates.
  • detergent compositions comprising an alkoxylated dianionic cleaning agent in combination with an enzyme, provide reduced soil redeposition benefits, in addition to improved cleaning performance, especially of greasy soils.
  • US-A-3, 832, 408 describes detergent compositions comprising 2- hydrocarbyl-l,4-butanediol ethoxylate disulfate in combination with high levels of phosphate builder.
  • US-A-3, 860,625 and US-A-3,634,269 describe 2-hydrocarbyl-l,4-butanediol ethoxylate disulfate as components of phosphate-free detergent compositions.
  • US-A-3, 959,334 and US-A-4,000,081 describe 2- hydrocarbyj- 1 ,4-butanediol disulfates said to be suitable as lime soap dispersants and a method for synthesizing these disulfates.
  • DE-A- 2,845,905 describes a process for continuous manufacture of butanediol-1 ,4 by catalytic hydrogenation of maleic anhydride.
  • a detergent composition comprising a) an alkoxylated dianionic cleaning agent comprising a structural skeleton of at least five carbon atoms to which two anionic substituent groups spaced at least three atoms apart, are attached, wherein at least one anionic substituent group is an alkoxy-linked sulfate group and the other is selected from the group consisting of sulfate and sulfonate group (preferably also alkoxy-linked); and
  • a first essential component of the cleaning compositions of the present invention is an alkoxylated dianionic cleaning agent.
  • the alkoxylated dianionic cleaning agent comprises a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart, are attached. At least one of said anionic substituent groups is an alkoxy-linked sulfate group; the other is a sulfate or sulfonate group, preferably a sulfate group linked by alkoxy moieties to the carbon structural skeleton.
  • Preferred alkoxy moieties include ethoxy and propoxy groups and combinations thereof.
  • the structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms.
  • the structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.
  • the structural skeleton comprises only carbon-containing groups and more preferably comprises only hydrocarbyl groups.
  • the structural skeleton comprises only straight or branched chain alkyl groups.
  • the structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulfate or sulfonate group attached to the branching).
  • the anionic substituent groups (which for purposes of counting positions along the structural skeleton, includes the alkoxy-linking moieties) present in the alkoxylated dianionic cleaning agents useful herein are spaced at a distance of at least three atoms from each other.
  • one anionic substituent group is attached to a carbon (the first carbon)
  • said first carbon is attached to a second carbon, which is in turn, attached to a third carbon and the third carbon is attached to die second anionic substituent group to give a spacing of three carbon atoms.
  • At least one alkoxy-linked anionic substituent group is substituted at a primary position on the strucmral skeleton.
  • the anionic substituent groups are preferably spaced 1- 3, 1-4, 1-5, 1-6 or greater apart; a 1-4 substitution for disulfated compounds is most preferred, and 1-4 and 1-5 substitution for sulfated/sulfonated compounds is most preferred.
  • 1-n substitution is to be interpreted such that 1 indicates an anionic substituent group (including any alkoxy-linking moieties) located at a given position on the structural skeleton and n indicates the number of atoms spaced between the first and second anionic substituent groups (including any alkoxy-linking moieties).
  • a preferred dianionic cleaning agent has the formula
  • R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C28, preferably C3 to C24, most preferably C ⁇ to C20 » or hydrogen;
  • a and B are independently selected from alkyl, substituted alkyl, and alkenyl group of chain length C 1 to C28 > preferably C ⁇ to C5, most preferably C ⁇ or C2, or a covalent bond;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, or mixed ethoxy /propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1;
  • a and B in total contain at least 2 atoms;
  • A, B, and R in total contain from 4 to 31 carbon atoms;
  • X and Y are anionic groups selected from the group consisting of sulfate and sulf
  • the most preferred alkoxylated dianionic cleaning agent has the formula as above where R is an alkyl group of chain length from C ⁇ Q to C ⁇ g, A and B are independently C ⁇ or C2, n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • Preferred alkoxylated dianionic cleaning agents herein include: ethoxylated and/or propoxylated disulfate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulfates, more preferably having the formulae:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about C ⁇ g; and n and m are independently within the range of from about 1 to about 10 (preferably from about 1 to about 5).
  • the alkoxylated dianionic cleaning agent is typically present at levels of incorporation of from about 0.1 % to about 40% , preferably from about 0.1 % to about 35 % , most preferably from about 0.5 % to about 15 % by weight of the liquid detergent composition.
  • the alkoxylated dianionic cleaning agent may also be present as a component of a surfactant system wherein the dianionic cleaning agent is present at levels of from 0.1 % to 99.9 % , preferably from 1 % to 60% , most preferably from 5 % to 40% by weight of the surfactant system.
  • the present invention compositions may also comprise some amount of sulfated alcohols and/or sulfonated alcohols which may comprise (to differing degrees depending on the reaction conditions used) a portion of the alkoxylated dianionic cleaning agent raw material used to manufacture the present invention compositions.
  • sulfated alcohols and/or sulfonated alcohols which may comprise (to differing degrees depending on the reaction conditions used) a portion of the alkoxylated dianionic cleaning agent raw material used to manufacture the present invention compositions.
  • Such alcohols are typically compatible with the present invention compositions and may be present as long as the requisite amount of alkoxylated dianionic cleaning agent is present in the final composition.
  • US-A-3, 959, 334 and US- A-4,000,081 describe 2-hydrocarbyl-l ,4-butanediol disulfates also prepared using a method involving the reduction of alkenyl succinic anhydrides with lithium aluminium hydride to produce either alkenyl or alkyl diols which are then sulfated.
  • These compounds may also be made by a method involving synthesis of the disulfated cleaning agent from a substituted cyclic anhydride having one or more carbon chain substituents having in total at least 5 carbon atoms comprising the following steps:
  • the cyclic anhydride starting material has a ring structure and comprises an acid anhydride linkage.
  • Cyclic anhydrides are generally formed by a ring forming condensation reaction of a single organic compound having a first carboxylic acid (-COOH) functional group and a second -COY functional group separated from the carboxylic acid functional group by at least two carbon atoms, wherein Y is usually an -OH, or halogen functionality.
  • a specific example of an organic compound which may be condensed to form a cyclic anhydride is maleic acid which on self-condensation provides maleic anhydride.
  • Maleic anhydride is readily available commercially.
  • the ring structure of the cyclic anhydride starting material contains from 4 to 7 carbon atoms, preferably from 4 to 6 carbon atoms in the ring structure.
  • Most preferably the cyclic anhydride starting material is based on succinic anhydride which has a 5-membered ring structure containing 4 carbon atoms in the ring.
  • the cyclic anhydride starting material is substituted by one or more carbon containing substituents, such that in total, these substitutents contain at least 5 carbon atoms, preferably from 5 to 25 carbon atoms, more preferably from 7 to 21 carbon atoms.
  • all of the carbon chain substituent(s) comprise either alkyl or alkenyl chains, which may be branched or unbranched. In one preferred aspect they are essentially unbranched. In another preferred aspect the chains are primarily monobranched, that is more than 50% by weight of the chains are monobranched.
  • the substituted cyclic anhydride has a single carbon chain substituent.
  • the substituted cyclic anhydride has two carbon chain substituents each having different points of attachment to the ring structure.
  • Substituted alkenylsuccinic and alkylsuccinic anhydrides are suitable starting materials herein.
  • Preferred anhydrides of this type have the following structures: R 2 o R 2 o
  • R and R2 are either H or an alkyl group.
  • R2 is H.
  • Linear alkenylsuccinic anhydrides may be obtained in high yield from the single stage 'ene reaction' of maleic anhydride with an alpha-olefin.
  • Branched alkenylsuccinic anhydrides may be obtained from the single stage 'ene reaction' of maleic anhydride with an internal olefin, such as those obtainable from the familiar SHOP (tradename of the Shell Co ⁇ oration) olefin making process.
  • Alkylsuccinic anhydride starting materials can be made by reducing alkenylsuccinic anhydrides. This reduction can be achieved under the conditions of the catalytic hydrogenation reduction step as described herein.
  • the first step is the reduction of the substituted cyclic anhydride to form a diol.
  • the reduction step comprises hydrogenation under pressure in the presence of a transition metal-containing hydrogenation catalyst.
  • the hydrogenation catalyst acts functionally to enhance the efficiency of the reductive hydrogenation process.
  • the catalyst is easy to regenerate.
  • the catalyst contains a transition metal selected from the group consisting of the group VIA (particularly Cr), VILA (particularly Mn), VIII (particularly Fe, Co, Ni, Ru, Rh, Pd, Pt) and IB (particularly Cu) elements.
  • Catalysts containing mixtures of any of these transition metals are envisaged as are catalysts containing other metals including the alkali and alkaline earth metals.
  • Copper-containing catalysts, particularly copper chromite are most preferred.
  • the hydrogenation catalyst may advantageously be supported on an inert support material.
  • the support material can generally comprise an oxide salt comprising a metal selected from the group consisting of aluminium, silicon and any mixtures thereof. Supports comprising aluminium oxide or silicon dioxide are especially preferred. Carbon and clay materials are also suitable supports.
  • the reductive hydrogenation step is carried out under pressure, and generally at elevated temperature. Usually a solvent is employed. This step can be carried out by a batch, continuous or vapor-phase process. A continuous process is preferred.
  • the pressure is typically from 1 x 10 ⁇ to 1 x 10? Pa, more preferably from 1 x 10 to 5 x 10 ⁇ Pa.
  • the temperature is generally from 150 to 350°C, more preferably from 200 to 300°C.
  • the time of reaction is generally from 30 minutes to 10 hours.
  • Suitable solvents include alcohols, particularly methanol, ethanol, propanol and butanol.
  • lactones are formed. These are however, convertible to diols by further catalytic hydrogenation. It may be advantageous to carry out the hydrogenation in two steps, preferably as part of a continuous step- wise process, such that a lactone is formed in the first step followed by a second step in which the lactone is reduced to the diol.
  • Conditions which favour lactone formation are high temperature ( - 300 °C) and low pressures ( — 1 x 10 ⁇ Pa). Any water formed during the hydrogenation will primarily be in the vapour phase, so that the anhydride is unlikely to be converted to a carboxylic acid which can inhibit the catalyst.
  • the best conditions for diol formation from the lactone are lower temperatures ( -220 °C) and high pressures ( - ⁇ 1 x 10? Pa), both of which conditions minimize the production of furan by-product.
  • Furans can be formed by a ring closure reaction of the diol product.
  • the tendency for such furans to form is greater at higher reaction temperatures and can be promoted by the transition-metal containing catalysts employed in the reduction step.
  • the formation of furans may therefore be minimzed by the use of lower reaction temperatures and by designing the process such that once formed the diol is removed from the catalytic environment.
  • the latter objective is met by the use of a continuous process whereby the reactants contact a high level of catalyst for a relatively short time and are then removed from the catalytic environment.
  • carboxylic acids which may be formed by certain ring-opening reactions of the cyclic anhydrides under the conditions of the reduction step can promote furan formation.
  • This problem can be alleviated by first forming the lactone in a separate step as mentioned above or by the use of an additional esterification step in which the cyclic anhydride is first treated with an alcohol, particularly methanol, in the presence of an esterification catalyst to form a diester. The diester is then converted to the diol via the reduction step.
  • the sulfation step may be carried out using any of the sulfation steps known in the art, including for example those described in US-A- 3,634,269, US-A-3, 959,334 and US-A-4,000,081.
  • the sulfation may be carried out in two stages where the first stage involves treatment of the diol with a sulfation agent, generally selected from the group consisting of chlorosulfonic acid, sulfur trioxide, adducts of sulfur trioxide with amines and any mixtures thereof.
  • the second stage involves neutralization, which is generally carried out using NaOH.
  • the reactor utilized is an electrically heated 500 ml (39 mm internal diameter x 432 mm internal length) Autoclave Engineers type 316 (tradename) stainless steel rocking autoclave fitted with an internal thermocouple and valving for periodic sampling of reaction mixtures.
  • the reactor is charged with 50 ml of alcohol solvent and 5 grams of copper chromite catalyst, as sold by Engelhardt under the tradename CU-1885P, that had been washed several times with high purity water then several times with alcohol solvent.
  • the reactor and contents are then heated to 250 °C at a hydrogen pressure of 2.4 x 10 ⁇ Pa and held for 1 hour.
  • the reactor is then cooled and charged (without exposing the catalyst to air) with 20 grams of the cyclic anhydride starting material and an additional 50 ml of alcohol solvent.
  • the process is carried out under different conditions of pressure and temperature, and with varying reaction times. Details of different reaction conditions are summarized in the table below:
  • the sulfation step is carried out, in each case, on the 1,4-alkyl diol product obtained from the reduction step.
  • Chlorosulfonic acid is used which results in a high yield (typically > 90%) of the required C ⁇ 4 alkyl 1 ,4 disulfate end-product as shown below: R.
  • R a heptyl group
  • Synthesis Example III Preparation of Alkyl 1.4-Sulfate/Sulfonates 1 ,4-dialcohol starting materials are first prepared as described hereinbefore by reduction of alkenyl succinic anhydrides. The desired compounds are then prepared following the reaction sequence as follows (wherein R can be alkyl or alkenyl, Cg to C20 ) :
  • This paper illustrates Steps 1 and 2 for several 1,2-, 1,3-, and 1 ,4-dialcohols, and also illustrates the opening of cyclic sulfates with phenoxide and fluoride anions.
  • this reaction sequence is not limited to the preparation of 1,4- sulfate/sulfonates, but may also be followed for the preparation of 1 ,3-sulfate/sulfonates from the corresponding 1,3-dialcohols.
  • Enzyme A second essential component of the detergent compositions is an enzyme.
  • Suitable enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Preferred enzymes are discussed in US Patents 3,519,570 and 3,533, 139.
  • 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, whitening, deodorizing, or freshness improving effect on substrates. In practical terms for current commercial preparations, typical amounts are up to 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 from 0.01 % to 1 % by weight of a commercial enzyme preparation.
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease A as disclosed in EP 130,756 A, January 9, 1985
  • 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.
  • Other preferred proteases include those of WO 9510591 A to Procter & Gamble.
  • a protease having decreased abso ⁇ tion and increased hydrolysis is available as described in WO 9507791 to Procter and 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, +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.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl fungamyl and BAN by Novo Industries A/S.
  • 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.
  • 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. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • 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 incorporated WO 9402597, Novo, Feb.
  • Methionine (Met) was identified as the most likely- residue to be modified. 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.
  • 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.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5 % by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas- fluorescens . Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from
  • This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989. Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • 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.
  • the weight ratio of dianionic cleaning agent to an enzyme is preferably from 300: 1 to 1 : 10, more preferably from 100: 1 to 1 :8, most preferably from 50: 1 to 1 :5.
  • the detergent compositions of the invention may also contain additional detergent components.
  • additional detergent components and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
  • compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, builders, alkalinity system, organic polymeric compounds, enzyme stabilising system, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • additional detergent components selected from surfactants, bleaches, builders, alkalinity system, organic polymeric compounds, enzyme stabilising system, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • a preferred component of the 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 stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • the detergent compositions of the invention preferably contain one or more surfactants selected from anionic, nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • the surfactant is preferably present as a component of a surfactant system at a level of from 0.1 % to 50% , more preferably from 1 % to 40% by weight, most preferably from 5% to 30% by weight of the surfactant system.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially rs) diesters of sulfosuccinate diesters), N-acyl sarcosinates. also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic mono-sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl mono-sulfates, alkyl ethoxymono-sulfates, fatty oleoyl glycerol mono-sulfates, alkyl phenol ethylene oxide ether mono-sulfates, the C5- 7 acyl-N-(C ⁇ -C4 alkyl) and - N-(Ci-C2 hydroxy alkyl) glucamine mono-sulfates, and mono-sulfates of alkylpolysaccharides such as the mono-sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl mono-sulfate surfactants are preferably selected from the linear and branched primary C ⁇ Q-C ⁇ g alkyl mono-sulfates, more preferably the Cn- C15 branched chain alkyl mono-sulfates and the C 12- 4 linear chain alkyl mono-sulfates.
  • Alkyl ethoxymono-sulfate surfactants are preferably selected from the group consisting of the o-C 18 alkyl mono-sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxymono-sulfate surfactant is a C ⁇ -Cis, most preferably Ci 1- 5 alkyl mono-sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl mono-sulfate and alkyl ethoxymonosulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. ⁇ n
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefm sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixmres thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxy lates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2COO-M+ wherein R is a C6 to C18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-0)-R3 wherein R is a CO to C18 alkyl group, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixmres thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixmres thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l- undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl- 1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors. Alkali metal sarcosinate surfactant
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C 1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C 1-C4 alkyl group
  • M is an alkali metal ion.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxy lated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Nonionic polyhydroxy fatty acid amide surfactant Nonionic polyhydroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the strucmral formula R 2 CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2- hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C [ alkyl (i.e.
  • R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C 19 alkyl or alkenyl, more preferably straight-chain C9- C17 alkyl or alkenyl, most preferably straight-chain C11-C 17 alkyl or alkenyl, or mixmre thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixmres thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • End-capped nonionic surfactants include essentially any nonionic surfactant comprising a branched chain alkyl or substituted alkyl group. Suitable end- capped nonionics include end-capped Butyl-polypropylene glycol ethyl ether described in GB l,221,217and end-capped polyethylene glycol ether describes in US 5,205,959.
  • Preferred end-capped nonionic surfactants include the alkoxylated and alkoxylated alcohol nonionic end-capped surfactants.
  • a preferred embodiment of the present invention is a mixed surfactant system comprising an end-capped nonionic and a polyhydroxy fatty acid amide.
  • the resulting mixed surfactant systems surprisingly exhibit low sudsing benefits.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR 4 ) x N°(R 5 )2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixmres thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixmres thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Cio-Cis alkyl dimethylamine oxide, and CiO-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2COO- wherein R is a C6-C18 hydrocarbyl group, each R 1 is typically C 1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2- 18 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C -Ci ⁇ , preferably C ⁇ -C o N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • the detergent compositions of the present invention preferably contain a detergency builder compound.
  • Suitable builder compound include water- soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxy lates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixmres of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1,2,2-ethane tetracarboxy lates, 1 , 1 , 3, 3 -propane tetracarboxylates and 1 , 1,2,3-propane tetracarboxy lates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxy lates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixmres thereof with their salts, e.g. citric acid or citrate/citric acid mixmres are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent compositions of the invention may optionally contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula
  • XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [A102) 12 (Si0 2 )l2J - *H2 ⁇
  • Zeolite X has the formula Na86 [(Al ⁇ 2)86(Si ⁇ 2)l06J- 276 H2O.
  • Zeolite MAP as disclosed in EP-B- 384,070 is a preferred zeolite builder herein.
  • a preferred feamre of detergent compositions of the invention is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixmres of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts-are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5 % to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixmres thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably inco ⁇ orated at a level of from 0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5 % to 10% by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g. , a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substimted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substimted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5- tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxy benzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substimted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substimted bleach activator compounds of this type are described in EP- A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substimted and unsubstimted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substimted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N- benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substimted may be a perbenzoic acid, or substimted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substimted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451 ; 4,397,757; 5,269,962; 5, 127,852; 5,093,022;
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substimted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substimted compounds of the following general formulae:
  • R* is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substimted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • Bleach catalyst The compositions optionally contain a transition metal containing bleach catalyst.
  • a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron, cobalt or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetre (methylenephosphonic acid) and water-soluble salts thereof.
  • ethylenediaminetetraacetic acid ethylenediaminetetre (methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn ⁇ 2( u -0)3(l ,4,7-trimethyl-l,4,7- triazacyclononane)2-(PF6)2, MnIH2( u -0)l( u -OAc)2(1.4,7-trimethyl-l ,4,7- triazacyclononane)2-(C104)2, Mn ⁇ 4(u-0)6(1 ,4,7-triazacyclononane)4- (CI ⁇ 4)2, Mn ⁇ iMnIV 4 ( u -0) ⁇ (u-OAc)2-(l ,4,7-trimethyl-l ,4,7- triazacyclononane)2-(C104)3, and mixmres thereof.
  • ligands suitable for use herein include l ,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl-l ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, l ,2,4,7-tetramethyl-l ,4,7-triazacyclononane, and mixmres thereof.
  • bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5, 194,416 which teaches mononuclear manganese _(IN) complexes such as Mn(l ,4,7-trimethyl-l ,4,7- triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5, 114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • binuciear Mn complexed with tetra- ⁇ -dentate and bi- ⁇ -dentate ligands including 4Mn III (u-0)2Mn IV ⁇ 4) +and [Bipy2MnIH(u- 0)2MnIVbipy 2 ]-(C104)3.
  • bleach catalysts are described, for example, in European patent application No. 408, 131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711 ,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601 ,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4, 119,557 (ferric complex catalyst), German Pat.
  • An optional component of the detergent compositions is from 1.5 % to 95% , preferably from 5% to 60%, most preferably from 10% to 40% by weight of the composition of an alkalinity system comprising components capable of providing alkalinity species in solution.
  • alkalinity species it is meant for the purposes of this invention: carbonate, bicarbonate, hydroxide and the various silicate anions.
  • alkalinity species can be formed for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixmres thereof are dissolved in water.
  • Alkali metal percarbonate and persilicate salts are also suitable sources of alkalinity species.
  • the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005 % to 20%, preferably from 0.1 % to 10% , more preferably from 0.25% to 7.5 % and most preferably from 0.5 % to 5 % by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy- ethylene 1 , 1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N' -disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399, 133.
  • iminodiacetic acid-N-2-hydroxy propyl sulfonic acid and aspartic acid N- carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516, 102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N- N'-diglutaric acid (EDDG) and 2-hydroxypro ⁇ ylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.
  • Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5 % to 15 %, most preferably from 1 % to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05 % to 10% , most preferably from 0.1 % to 5 % by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixmres of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 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.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ g-C40 ketones (e.g. stearone) 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, bis stearic acid amide and monostearyl di- alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5 % to 25 % by weight of the silicone/silica antifoam compound;
  • silica/silicone antifoam compound is incorporated at a level of from 5% to 50% , preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5 % to 10% , preferably 1 % to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;
  • an inert carrier fluid compound most preferably comprising a Ci ⁇ - C i g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80% , preferably 10% to 70% , by weight;
  • a highly preferred particulate suds suppressing system is described in EP- A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A- 0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixmre thereof, with a melting point of from 45 °C to 80°C.
  • the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP- A-313, 146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • Polymeric dve transfer inhibiting agents may also comprise from 0.01 % to 10% , preferably from 0.05 % to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • Rl , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially available from ISP Co ⁇ oration. New York, NY and Montreal. Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Co ⁇ oration.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005 % to 5 % by weight of certain types of hydrophilic optical brighteners-.
  • Hydrophilic optical brighteners useful herein include those having the strucmral formula:
  • Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4' ,-bis[(4-anilino-6-(N-2- bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration.
  • Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • R ⁇ is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s- triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • Cationic fabric softening agents can also be inco ⁇ orated into compositions in accordance with the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Cationic fabric softening agents are typically inco ⁇ orated at total levels of from 0.5% to 15% by weight, normally from 1 % to 5 % by weight.
  • Other optional ingredients are typically inco ⁇ orated at total levels of from 0.5% to 15% by weight, normally from 1 % to 5 % by weight.
  • compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions preferably have a pH measured as a 1 % solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0.
  • compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • Dianionic cleaning agent agglomerate particles
  • the dianionic cleaning agent herein is preferably present in granular compositions in the form of dianionic cleaning agent agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • the most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active dianionic cleaning agent pastes and to control the particle size of the resultant agglomerates within specified limits.
  • Such a process involves mixing an effective amount of powder with a high active dianionic cleaning agent paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufacmred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D- 4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high active dianionic cleaning agent paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufacmred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau
  • a high active dianionic cleaning agent paste comprising from 50% by weight to 95 % by weight, preferably 70% by weight to 85 % by weight of surfactant is typically used.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the dianionic cleaning agent used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the dispensing device containing the detergent product is placed inside the drum.
  • water is introduced into the drum and the drum periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.
  • An article by J. Bland published in Manufacmring Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette” .
  • Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/ 11562.
  • Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070.
  • the latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
  • the support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • C25E5 A C 12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide
  • Nonionic C 13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxy lation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH (low foaming)
  • Nai2(A102Si ⁇ 2)i2- 27H2 ⁇ having a primary particle size in the range from 0.1 to 10 micrometers
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
  • Bismuth nitrate Bismuth nitrate salt PA30 Polyacrylic acid of average molecular weight approximately 8,000 Te ⁇ olymer Te ⁇ olymer of average molecular weight approx.
  • Brightener 1 Disodium 4.4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-1.3.5- triazin-2-yl)amino) stilbene-2 :2 ' -disulfonate .
  • SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone
  • SRP 2 Diethoxylated poly (1 , 2 propylene terephtalate) short block polymer
  • laundry detergent compositions A to F were prepared in accord with the invention:
  • Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • liquid detergent formulations according to the present invention were prepared:
  • detergent composition tablets in accord with the present invention of 25g weight were prepared by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm ⁇ using a standard 12 head rotary press:

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention porte sur une composition détergente comportant un agent de nettoyage dianionique alkoxylé et une enzyme.
PCT/US1997/010804 1996-06-28 1997-06-27 Composition detergente WO1998000502A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2083596P 1996-06-28 1996-06-28
US60/020,835 1996-06-28

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WO1998000502A2 true WO1998000502A2 (fr) 1998-01-08
WO1998000502A3 WO1998000502A3 (fr) 1998-04-23

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049585A (en) * 1974-12-30 1977-09-20 The Procter & Gamble Company Detergent compositions containing internal vicinal disulfates
GB8404120D0 (en) * 1984-02-16 1984-03-21 Unilever Plc Liquid detergent compositions
JPH01161095A (ja) * 1987-12-17 1989-06-23 Lion Corp 洗浄剤組成物
FR2733982B1 (fr) * 1995-05-11 1997-06-13 Rhone Poulenc Chimie Alkyl ether sulfates oligomeriques et leurs utilisations dans des compositions nettoyantes

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