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EP0832965A1 - Compositions pour trempage - Google Patents

Compositions pour trempage Download PDF

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Publication number
EP0832965A1
EP0832965A1 EP96870123A EP96870123A EP0832965A1 EP 0832965 A1 EP0832965 A1 EP 0832965A1 EP 96870123 A EP96870123 A EP 96870123A EP 96870123 A EP96870123 A EP 96870123A EP 0832965 A1 EP0832965 A1 EP 0832965A1
Authority
EP
European Patent Office
Prior art keywords
soaking
group
cleaning agent
alkyl
anionic substituent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96870123A
Other languages
German (de)
English (en)
Inventor
Gabriella Ardia (Nmn)
Lamberto Biscarini (Nmn)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP96870123A priority Critical patent/EP0832965A1/fr
Priority to JP10515964A priority patent/JP2000503066A/ja
Priority to CA002267338A priority patent/CA2267338A1/fr
Priority to MA24811A priority patent/MA24330A1/fr
Priority to ZA9708677A priority patent/ZA978677B/xx
Priority to PL97332646A priority patent/PL332646A1/xx
Priority to ARP970104456A priority patent/AR010228A1/es
Priority to AU47389/97A priority patent/AU4738997A/en
Priority to BR9713474-0A priority patent/BR9713474A/pt
Priority to PCT/US1997/017370 priority patent/WO1998013455A1/fr
Publication of EP0832965A1 publication Critical patent/EP0832965A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters

Definitions

  • the present invention relates to the cleaning of fabrics in soaking conditions, i.e., in conditions where the fabrics are left to soak in a soaking liquor comprising water and detergent ingredients, either as a first step before a typical washing operation, or as a single step.
  • Fabric soaking operations have been described in the art.
  • fabrics are left in contact with a soaking liquor for a prolonged period of time typically ranging from more than 1 hour to overnight or even 24 hours.
  • This laundering process has the advantage that it maximises the contact time between the fabrics and the key active ingredients of the soaking liquor. It also has the advantage that it reduces or eliminates the need for a typical laundering operation involving the need for mechanical agitation, or that it improves the efficiency of the subsequent typical laundering operation.
  • Such soaking operations are typically desirable to remove tough outdoor dirt from fabrics, such as particulate soil like mud, silt and/or clays.
  • clays usually have a microcrystalline mineral structure (e.g., hydrous aluminium silicate like illite, montmorillonite, kaolinite and the like) with the presence of an organic fraction.
  • the organic fraction can contain a variety of compounds (e.g., humic acid, fulvic acid, plant/animal biomass and the like).
  • Clays can also contain several kinds of metals (e.g., magnesium, calcium, potassium, iron and the like).
  • metals e.g., magnesium, calcium, potassium, iron and the like.
  • particulate soil is particularly difficult to remove from fabrics. Indeed, it is believed that the very fine dirt grains like clays or silt, typically below 0.002 mm in size, can insert among fabric fibers and steadily stick to the surface of the fibers. This problem is particularly acute with socks which are most exposed to silt and clay pick-up. Also, such soaking operations are not fully satisfactory regarding the enzymatic stain removal performance.
  • Enzymatic stains are typically composed of carbohydrates and proteinaceus soil like blood. It has now been observed that enzymatic stains may act as a glue for particulate soil on fabrics, thus removing such enzymatic stains may facilitate the removal of particulate soil from fabrics.
  • a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent in a soaking composition, delivers improved stain removal performance on tough outdoor dirt like particulate soil and/or enzymatic stains under soaking conditions (i.e., when left in contact for a prolonged period of time typically more than 1 hour up to 24 hours), as compared to the stain removal performance delivered with the same composition being free of a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent.
  • the present invention encompasses a process of soaking fabrics, wherein said fabrics are immersed for more than one hour in a soaking liquor comprising water and an effective amount of a composition comprising a dianionic cleaning agent, as defined herein, and/or an alkoxylated dianionic cleaning agent, as defined herein, then removed from said soaking liquor.
  • An advantage of the present invention is that the stain removal performance, when soaking a fabric in presence of a soaking composition comprising an alkoxylated dianionic cleaning agent and/or a dianionic cleaning agent, is improved even in the presence of relatively high levels of hardness ions.
  • hardness ions calcium or magnesium ions
  • Anionic surfactants are especially sensitive to hardness ions, reducing surfactant performance, eventually precipitating the surfactant from the soaking liquor as a calcium or magnesium salt. This phenomen occurs less when using a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent.
  • the soaking detergent manufacturer may make use of builders which are not the more performing at sequestering free hardness ions, and thus may use less expensive builders in such a soaking composition.
  • the stain removal performance on particulate soil and/or enzymatic stains is further improved by combining said dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent with a sorbitan ester, as defined hereinafter, in a soaking detergent composition.
  • the present invention encompasses a soaking detergent composition comprising a sorbitan ester and, a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent, as defined herein, as well as a process of soaking fabrics in a soaking liquor formed with said soaking detergent composition.
  • compositions of the present invention comprising said dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent together with a sorbitan ester, provide effective stain removal performance on other types of stains like greasy stains, e.g., bacon, grease, spaghetti sauce and/or bleachable stains like tea and/or coffee.
  • US 3 755 201 discloses a laundry product with a blue dye stuff, surfactants, a compound selected from the group of builders, fillers, solvents and adjuvants. These compositions may be employed in pre-soaking laundry products.
  • Polyoxyethylene sorbitan monostearate is disclosed.
  • No dianionic cleaning agents and/or alkoxylated dianionic cleaning agents are disclosed.
  • US 3 762 859 discloses laundry detergent compositions comprising surfactants, and particular dyestuff. Sorbitan esters like sorbitan monolaurate, sorbitan mono-oleate and mannitan monopalmitate are disclosed. No dianionic cleaning agents and/or alkoxylated dianionic cleaning agents are disclosed.
  • the present invention encompasses a soaking composition comprising:
  • the present invention further encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of a composition as described hereinabove, for an effective
  • the present invention encompasses a process of soaking fabrics, wherein said fabrics are immersed for more than one hour in a soaking liquor comprising water and an effective amount of a composition comprising a dianionic cleaning agent, as defined herein, and/or an alkoxylated dianionic cleaning agent, as defined herein, then removed from said soaking liquor.
  • the present invention encompasses a composition and a process of soaking fabrics.
  • the composition hereinafter referred to as the soaking composition is used in the soaking process.
  • the present invention encompasses a composition which comprises a sorbitan ester, and a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent.
  • the first essential ingredient of the compositions of the present invention is a sorbitan ester according to the formula C 6 H 9 O 2 (C 2 H 4 O) x R 1 R 2 R 3, wherein x is an integer of from 0 to 40, R 1 , R 2 are independently OH or (C n H n+1 )COO, and R 3 is (C n H n+1 )COO group, where n is an integer of from 11 to 17.
  • x is 0 or 20
  • the most preferred compositions herein comprise polyethoxylated (20) sorbitan tristearate, i.e. C 6 H 9 O 2 (C 2 H 4 O) 20 (C 17 H 35 COO) 3 , or polyethoxylated (20) sorbitan monostearate, i.e. C 6 H 9 O 2 (C 2 H 4 O) 20 (OH) 2 (C 17 H 35 COO), or sorbitan monostearate, i.e. C 6 H 9 O 2 (OH) 2 (C 17 H 35 COO), or sorbitan monopalmitate, i.e. C 6 H 9 O 2 (OH) 2 (C 15 H 31 COO), or mixtures thereof.
  • Glycosperse TS 20 from Lonza (polyethoxylated sorbitan tristearate)
  • Glycosperse S 20 from Lonza (polyethoxylated sorbitan monostearate)
  • Radiasurf 7145 from Fina from sorbitan monostearate
  • Radiasurf 7135 from Fina (sorbitan monopalmitate)
  • Armotan MP from Akzo (sorbitan monopalmitate).
  • the soaking composition herein there should be from 0.01% to 10% of the total composition of said sorbitan ester or mixtures thereof, preferably from 0.01% to 5%, most preferably from 0.5% to 5%.
  • the second essential ingredient of the compositions of the present invention is a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent.
  • the 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 a sulfate group; the other is a sulfate or sulfonate group, preferably a sulfate group.
  • Said 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 preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms.
  • 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 present in the 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 the second anionic substituent group to give a spacing of three carbon atoms.
  • At least one anionic substituent group is substituted at a primary position on the structural 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 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.
  • a preferred dianionic cleaning agent has the formula where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C 1 to C 28 , preferably C 3 to C 24 , most preferably C 8 to C 20 , or hydrogen;
  • a and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length C 1 to C 28 , preferably C 1 to C 5 , most preferably C 1 or C 2 , or a covalent bond, and 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 sulfonate, provided that at least one of X or Y is a sulfate group; and
  • M is a cationic moiety, preferably a substituted or unsubstitute
  • the most preferred dianionic cleaning agent has the formula as above where R is an alkyl group of chain length from C 10 to C 18 , A and B are independently C 1 or C 2 , both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • the dianionic cleaning agent is typically present at levels of incorporation of from 0.01% to 50%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, and most preferably from 0.2% to 2% by weight of the soaking composition.
  • Preferred dianionic cleaning agents herein include:
  • 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 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 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 dianionic cleaning agent is present in the final composition.
  • 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 substituents 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: where R and R 2 are either H or an alkyl group. In one preferred aspect R 2 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 Corporation) 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), VIIA (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.
  • Platinum, paladium, and copper-containing catalysts, particularly copper chromite are most preferred.
  • An alternate synthesis may also utilize supported Pd/Rh catalysts to selectively hydrogenate maleic anhydride to either THF of butane diol, as described by S.B. Ziernecki, C&EN, April 3, 1995, pp 20-23.
  • 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 5 to 1 x 10 7 Pa, more preferably from 1 x 10 6 to 5 x 10 6 Pa.
  • the temperature is generally from 150°C to 350°C, more preferably from 200°C 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 5 Pa). Any water formed during the hydrogenation will primarily be in the vapour phase, so that the anhydride is unlikely to be converted into 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 7 Pa), both of which conditions minimise 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 minimised 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 6 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 summarised in the table below: Example No. Pressure (10 6 Pa) Temp.
  • 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 14 alkyl 1,4 disulfate end-product as shown below:
  • R a heptyl group
  • 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, C 8 to C 20 ):
  • This reaction scheme is described in part in greater detail in Berridge, et. al., (J. Org. Chem. 1990, 55, 1211).
  • 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.
  • the alkoxylated dianionic cleaning agent to be used herein 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.
  • Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.
  • Preferred alkoxy moieties are ethoxy, propoxy, 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 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 the 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 structural 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.
  • 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 alkoxylated dianionic cleaning agent has the formula where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C 1 to C 28 , preferably C 3 to C 24 , most preferably C 8 to C 20 , or hydrogen; A and B are independently selected from alkyl, substituted alkyl, and alkenyl group of chain length C 1 to C 28 , preferably C 1 to C 5 , most preferably C 1 or C 2 , or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from 0 to 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 consist
  • the most preferred alkoxylated dianionic cleaning agent has the formula as above where R is an alkyl group of chain length from C 10 to C 18 , A and B are independently C 1 or C 2 , n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • the alkoxylated dianionic cleaning agent is typically present at levels of incorporation of from 0.01% to 50%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, and most preferably from 0.2% to 2% by weight of the soaking composition.
  • 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: wherein R is a straight or branched chain alkyl or alkenyl group of chain length from C6 to C 18 ; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and n and m are independently within the range of from 0 to 10 (preferably from 0 to 5), with at least m or n being 1.
  • 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-3,832,408 and US-A-3,860,625 describe 2-alkyl or alkenyl-1,4-butanediol ethoxylate disulfates prepared by the reduction of alkenyl succinic anhydrides with lithium aluminum hydride to produce either alkenyl or alkyl diols which are then ethoxylated prior to sulfation.
  • US-A-3,634,269 describes 2-alkyl or alkenyl-1,4-butanediol disulfates prepared by the reduction of alkenyl succinic anhydrides with lithium aluminum hydride to produce either alkenyl or alkyl diols which are then sulfated.
  • US-A-3,959,334 and US-A-4,000,081 describe 2-hydrocarbyl-1,4-butanediol disulfates also prepared using a method involving the reduction of alkenyl succinic anhydrides with lithium aluminum 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 starting material i.e., said substituted cyclic anhydride
  • the reduction of said starting material to form a diol may be performed as for the synthesis method of a dianionic cleaning agent described herein before.
  • the diol is then alkoxylated prior to the sulfation step, such that alkoxylated disulfate cleaning agents are obtained as the final product.
  • alkoxylated disulfate cleaning agents are obtained as the final product.
  • Suitable methods for the alkoxylation of diols are described in US Patents 3,832,408 and 3,860,625 noted hereinbefore.
  • the condensation products of the diols with from 1 to 25 moles, preferably from 2 to 10 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are preferred herein.
  • the sulfation step may be carried out using any of the sulfation steps known in the art as already described hereinbefore in the synthesis method of the dianionic cleaning agents herein.
  • 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 6 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 summarised in the table below: Example No. Pressure (10 6 Pa) Temp.
  • This diol is then treated with an excess of ethylene oxide to give the ethoxylated diol.
  • the sulfation step is then 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 14 alkyl 1,4 ethoxylated disulfate end-product.
  • R a heptyl group
  • the compositions according to the present invention may further comprise an oxygen bleach.
  • oxygen beaches provide a multitude of benefits such as bleaching of stains, deodorization, as well as disinfectancy, and the sorbitan esters and (alkoxylated) dianionic cleaning agents according to the present invention have a further particular advantage that they are resistant to oxydation by oxygen bleaches.
  • the oxygen bleach in the composition may come from a variety of sources such as hydrogen peroxide or any of the addition compounds of hydrogen peroxide, or organic peroxyacid, or mixtures thereof.
  • addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.
  • a second chemical compound which may be for example an inorganic salt, urea or organic carboxylate
  • the addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide forms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
  • oxygen beaches include persulphates, particularly potassium persulphate K 2 S 2 O 8 and sodium persulphate Na 2 S 2 O 8 .
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • alkali metal salt of percarbonate, perborate or mixtures thereof are the preferred inorganic perhydrate salts for use herein.
  • Preferred alkali metal salt of percarbonate is sodium percarbonate.
  • Soaking compositions in the present invention may comprise from 0.01% to 80% by weight of the total composition of an oxygen bleach or mixtures thereof, preferably from 5% to 45% and more preferably from 10% to 40%.
  • the soaking compositions herein comprise an oxygen bleach
  • bleach activators typically up to a level of 30% by weight of the total composition. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231.
  • Preferred examples of such compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent application 91870207.7.
  • TAED tetracetyl ethylene diamine
  • NOBS n-nonanoyloxybenzenesulphonate
  • ATC acetyl triethyl citrate
  • N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam.
  • the soaking compositions herein may comprise mixtures of said bleach activators.
  • Preferred mixtures of bleach activators herein comprise n-nonanoyloxybenzenesulphonate (NOBS) together with a second bleach activator having a low tendency to generate diacyl peroxide, but which delivers mainly peracid.
  • Said second bleach activators may include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactam and the like, or mixtures thereof.
  • mixtures of bleach activators comprising n-nonanoyloxybenzenesulphonate and said second bleach activators, allow to boost particulate soil cleaning performance while exhibiting at the same time good performance on diacyl peroxide sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. body soils).
  • diacyl peroxide sensitive soil e.g. beta-carotene
  • peracid sensitive soil e.g. body soils
  • the soaking compositions herein may comprise from 0% to 15% by weight of the total composition of n-nonanoyloxybenzenesulphonate, preferably from 1% to 10% and more preferably from 3% to 7% and from 0% to 15% by weight of the total composition of said second bleach activator preferably from 1% to 10% and more preferably from 3% to 7%.
  • compositions herein may comprise an acidifying system amongst the preferred optional ingredients.
  • the purpose of said acidifying system is to control the alkalinity generated by the source of available oxygen and any alkaline compounds present in the wash solution.
  • Said system comprises anhydrous acidifying agent, or mixtures thereof, which needs to be incorporated in the product in an anhydrous form, and to have a good stability in oxidizing environment.
  • Suitable anhydrous acidifying agents for use herein are carboxylic acids such as citric acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic acid or their salts or mixtures thereof.
  • Other suitable acidifying agents include sodium bicarbonate, sodium sesquicarbonate and silicic acid.
  • citric acid can be used in its acidic form or in the form of its salts (mono-, di-, tri- salts) and in all its anhydrous and hydrated forms, or mixtures thereof. It may additionally act as a builder and a chelant, and it is biodegradable.
  • the compositions according to the present invention comprise from up to 20% by weight of the total composition of anhydrous citric acid, preferably from 5% to 15%, most preferably about 10%.
  • compositions herein may comprise an alkali metal salt of silicate, or mixtures thereof, amongst the preferred optional ingredients.
  • Preferred alkali metal salt of silicate to be used herein is sodium silicate.
  • the soaking compositions comprise an oxygen bleach, it has been found that the decomposition of available oxygen produced in the soaking liquors upon dissolution of the soaking compositions is reduced by the presence of at least 40 parts per million of sodium silicate in said soaking liquors.
  • alkali metal salt of silicate can be used herein, including the crystalline forms as well as the amorphous forms of said alkali metal salt of silicate or mixtures thereof.
  • Suitable crystalline forms of sodium silicate to be used are the crystalline layered silicates of the granular formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • M is sodium and y is 0 and preferred examples of this formula comprise the a , b , g and d forms of Na 2 Si 2 O 5.
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is d - Na 2 Si 2 O 5, NaSKS-6.
  • Crystalline layered silicates are incorporated in soaking compositions herein, either as dry mixed solids, or as solid components of agglomerates with other components.
  • Suitable amorphous forms of sodium silicate to be used herein have the following general formula: NaMSi x O 2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
  • M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
  • Preferred to be used herein are the amorphous forms of Si 2 O 5 Na 2 O.
  • Suitable Zeolites for use herein are aluminosilicates including those having the empirical formula: Mz(zAlO2.ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
  • Preferred zeolites which have the formula: Naz ⁇ (AlO2)z (SiO2)yù.xH2O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na12 ⁇ (AlO2)12(SiO2)12ù.xH2O wherein x is from 20 to 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • compositions herein may comprise from 0.5% to 15% by weight of the total composition of an alkali metal salt of silicate or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
  • composition herein may also comprise a builder amongst the preferred optional ingredients.
  • All builders known to those skilled in the art may be used herein.
  • Suitable phosphate builders for use herein include sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
  • Suitable polycarboxylate builders for use herein include ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,120,874 and 4,102,903.
  • Other useful detergency builders include the ether hydroxypolycarboxylates, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Suitable polycarboxylate buiders for use herein include builders according to formula I wherein Y is a comonomer or comonomer mixture; R 1 and R 2 are bleach- and alkali-stable polymer-end groups; R 3 is H, OH or C 1-4 alkyl; M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, or mixtures thereof.
  • the first category belongs to the class of copolymeric polymers which are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C 1-4 alkyl acrylic acid as second monomer.
  • the polymers belonging to said first class are those where p is not 0 and Y is selected from the acids listed hereinabove.
  • Preferred polymers of this class are those according to formula I hereinabove, where Y is maleic acid.
  • R 3 and M are H
  • n is such that the polymers have a molecular weight of from 1000 to 400 000 atomic mass units.
  • the second category of preferred polymers for use herein belongs to the class of polymers in which, referring to formula I hereinabove, p is 0 and R 3 is H or C 1-4 alkyl.
  • n is such that the polymers have a molecular weight of from 1000 to 400 000 atomic mass units.
  • R 3 and M are H.
  • alkali-stable polymer end groups R 1 and R 2 in formula I hereinabove suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.
  • n the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight.
  • n 182 (i.e. 15,500 / (116 x 0.3 + 72 x 0.7)).
  • highly preferred polymers for use herein are those of the first category in which n averages from 100 to 800, preferably from 120 to 400.
  • Preferred builders for use herein are polymers of maleic or acrylic acid, or copolymers of maleic and acrylic acid.
  • compositions of the present invention comprise up to 50% by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 20% and more preferably from 0.5% to 10%.
  • compositions according to the present invention may further comprise a soil suspending polyamine polymer or mixtures thereof, as optional ingredient.
  • a soil suspending polyamine polymer known to those skilled in the art may also be used herein.
  • Particularly suitable polyamine polymers for use herein are polyalkoxylated polyamines.
  • Such materials can conveniently be represented as molecules of the empirical structures with repeating units : wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R 1 may be a C 1 -C 20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20; n is an integer of at least 2, preferably from 2-20, most preferably 3-5; and X - is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • ethoxylated polyethylene amine in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylene diamine.
  • said soil suspending polyamine polymers contribute to the benefits of the present invention, i.e., that when added in a soaking composition comprising sorbitan ester and a dianionic cleaning agent and/or an alkoxylated dianionic cleaning agent, they further improve the stain removal performance of said composition. Indeed, they allow to improve the stain removal performance on a variety of stains including particulate soils, enzymatic stains as well as greasy stains and/or bleachable stains.
  • compositions of the present invention comprise up to 10% by weight of the total composition of such a soil suspending polyamine polymer or mixtures thereof, preferably from 0.1% to 5% and more preferably from 0.3% to 2%.
  • Suitable amino carboxylate cheating agents which may be used herein include diethylene triamino pentacetic acid, ethylenediamine tetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexaacetates, and ethanoldiglycines, alkali metal ammonium and substituted ammonium salts thereof or mixtures thereof.
  • chelating agents include ethylenediamine-N,N'-disuccinic acids (EDDS) or alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • other suitable chelating agents may be the organic phosphonates, including amino alkylene poly(alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or in the form of their metal alkali salt.
  • the organic phosphonate compounds where present are in the form of their magnesium salt.
  • the soaking compositions in the present invention may accordingly comprise from 0% to 5% by weight of the total compositions of said chelating agents, preferably from 0% to 3%, more preferably from 0.05% to 2%.
  • compositions herein may further comprise a filler like inorganic filler salts such as alkali metal carbonates, bicarbonates and sulphates.
  • a filler like inorganic filler salts such as alkali metal carbonates, bicarbonates and sulphates.
  • Such fillers for instance sodium bicarbonate, may also act as acidifying agent as described hereinbefore. Accordingly, sodium bicarbonate and sodium sulphate are the preferred filler materials for use herein.
  • compositions of the present invention comprise up to 50% by weight of the total composition of a filler or mixtures thereof, preferably from 0.1% to 15 % and more preferably from 1% to 6%.
  • Soaking compositions in the present invention may further comprise other optional ingredients such as surfactants, optical brighteners, enzymes, other chelants, dispersants, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments, perfumes and the like. Said optional ingredients can be added in varying amounts as desired.
  • compositions herein can be manufactured in solid, preferably granular, or even in liquid form.
  • the present invention encompasses processes of soaking fabrics. Indeed, the present invention encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of a composition as described hereinbefore, for an effective period of time, then removed from said soaking liquor.
  • the expression "process of soaking fabrics” refers to the action of leaving fabrics to soak in a soaking liquor comprising water and a composition as described hereinabove, for a period of time sufficient to clean said fabrics.
  • the soaking process herein allows prolonged contact time between the fabrics and the soaking liquor, typically up to 24 hours.
  • the soaking process can be performed independently from any other process, such as a typical laundering operation, or a first step before a second, typical laundering step.
  • fabrics are left to soak for a period of time ranging from 10 minutes to 24 hours, preferably from 30 min to 24 hours, more preferably more than 1 hour to 24 hours, even more preferable 2 hours to 24 hours, and most preferably 4 hours to 24 hours.
  • fabrics After the fabrics have been immersed in said soaking liquor for a sufficient period of time, they can be removed and rinsed with water.
  • the fabrics can also be washed in a normal laundering operation after they have been soaked, with or without having been rinsed in between the soaking operation and the subsequent laundering operation.
  • a soaking composition described hereinabove is diluted in an appropriate amount of water to produce a soaking liquor.
  • Suitable doses may range from 45 to 50 grams of soaking composition in 3.5 to 5 liters of water, down to 90 to 100 grams of soaking composition in 20 to 45 liters of water.
  • one dose is 45-50 grams in 3.5 to 5 liters for a concentrated soak (bucket/sink).
  • the dose is 90-100 grams in about 20 (Europe) to 45 (US) liters of water.
  • the fabrics to be soaked are then immersed in the soaking liquor for an appropriate period of time. There are factors which may influence overall performance of the process on particulate dirt/soils. Such factors include prolonged soaking time.
  • soaking time is overnight, i.e., 8 hours up to 24 hours, preferably 12 hours to 24 hours.
  • Another factor is the initial warm or warmluke temperature. Indeed, higher initial temperatures of the soaking liquors ensure large benefits in performance.
  • the process herein is suitable for cleaning a variety of fabrics, but finds a preferred application in the soaking of socks, which are particularly exposed to silt and clay pick-up.
  • the present invention also encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of a composition comprising a dianionic cleaning agent, as defined herein, and/or an alkoxylated dianionic cleaning agent, as defined herein, for more than 1 hour, preferably more than 2 hours and more preferably 4 hours to 24 hours, then removed from said soaking liquor.
  • a composition comprising a dianionic cleaning agent, as defined herein, and/or an alkoxylated dianionic cleaning agent, as defined herein, for more than 1 hour, preferably more than 2 hours and more preferably 4 hours to 24 hours, then removed from said soaking liquor.
  • the stain removal performance of a given composition on a soiled fabric under soaking conditions may be evaluated by the following test method. Soaking liquors are formed by diluting for instance 45 g of the soaking compositions herein in 3.78 liters of water or 90 g of the soaking composition in 45 liters of water. Fabrics are then immersed in the resulting soaking liquor for a time ranging from 30 minutes to 18 hours. Finally, the fabrics are removed from the soaking liquors, rinsed with water and washed with a regular washing process, handwash or washing machine wash, with a regular detergent, with or without re-using the soaking liquor, then said fabrics are left to dry.
  • typical soiled fabrics to be used in this stain removal performance test may be commercially available from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA, such as clay, grass, spaghetti sauce, gravy, dirty motor oil, make-up, barbecue sauce, tea, blood on two different substrates: cotton (CW120) and polycotton (PCW28).
  • EMC Electronic Manufacturing Company
  • CW120 cotton
  • PCW28 polycotton
  • the stain removal performance may be evaluated by comparing side by side the soiled fabrics pretreated with the composition according to the present invention with those pretreated with the reference, e.g., the same composition without such a dianionic cleaning agent or alkoxylated dianionic cleaning agent according to the present invention.
  • a visual grading scale may be used to assign differences in panel score units (psu), in a range from 0 to 4.
  • compositions are prepared by mixing the listed ingredients in the listed proportions.
  • Others Inerts and minors up to 100 up to 100 up to 100 up to 100
  • Soaking liquors are formed by diluting 45 g of each of the above compositions 1 to 12 in between 3.5 lit. to 5.0 lit. of water. 0.5 to 2 Kg of fabrics are then each time immersed in said soaking liquors for a time ranging from 10 minutes to 24 hours. Finally, the fabrics are removed from the soaking liquors, rinsed with water and washed with a regular washing process, handwash or washing machine wash, with a regular detergent, with or without re-using the soaking liquor, then said fabrics are left to dry. Excellent stain removal performance is obtained with these compositions on various stains including mud/clay stains, enzymatic stains, greasy stains, bleachable stains and the like.
  • Soaking liquors are formed by diluting 45 g of each of the above compositions 13 to 15 in between 3.5 lit. to 5.0 lit. of water. 0.5 to 2 Kg of fabrics are then each time immersed in said soaking liquors for more than 1 hour, typically 4 hours to 24 hours. Finally, the fabrics are removed from the soaking liquors, rinsed with water and washed with a regular washing process, handwash or washing machine wash, with a regular detergent, with or without re-using the soaking liquor, then said fabrics are left to dry. Good stain removal performance is obtained with these processes on various stains including mud/clay stains, enzymatic stains, greasy stains, bleachable stains and the like.

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CA002267338A CA2267338A1 (fr) 1996-09-27 1997-09-26 Compositions de trempage
MA24811A MA24330A1 (fr) 1996-09-27 1997-09-26 Composition et procede de trempage de tissus
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PL97332646A PL332646A1 (en) 1996-09-27 1997-09-26 Laundry soaking composition
ARP970104456A AR010228A1 (es) 1996-09-27 1997-09-26 Composiciones para el remojo y proceso utilizando dichas composiciones
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WO2002020473A1 (fr) * 2000-09-04 2002-03-14 The Court Of Napier University Tensioactif
EP0861885B1 (fr) * 1997-02-27 2003-04-16 The Procter & Gamble Company Compositions pour trempage
WO2020216705A1 (fr) * 2019-04-23 2020-10-29 Unilever Plc Systèmes tensioactifs

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GB1540301A (en) * 1975-11-03 1979-02-07 Johnson & Johnson Detergent composition
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WO1996007473A1 (fr) * 1994-09-09 1996-03-14 Henkel Kommanditgesellschaft Auf Aktien Melanges de detergents doux
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US3850854A (en) * 1966-07-12 1974-11-26 Lever Brothers Ltd Novel detergent composition
FR2289606A1 (fr) * 1974-11-01 1976-05-28 Procter & Gamble Compositions de conditionnement de tissus
GB1540301A (en) * 1975-11-03 1979-02-07 Johnson & Johnson Detergent composition
EP0590521A1 (fr) * 1992-10-01 1994-04-06 Tomei Sangyo Kabushiki Kaisha Solution aqueuse pour le nettoyage et la conservation de lentilles de contact et procédé pour nettoyer et désinfecter une lentille de contact au moyen d'une telle solution
WO1996007473A1 (fr) * 1994-09-09 1996-03-14 Henkel Kommanditgesellschaft Auf Aktien Melanges de detergents doux
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Publication number Priority date Publication date Assignee Title
EP0861885B1 (fr) * 1997-02-27 2003-04-16 The Procter & Gamble Company Compositions pour trempage
WO2002020473A1 (fr) * 2000-09-04 2002-03-14 The Court Of Napier University Tensioactif
WO2020216705A1 (fr) * 2019-04-23 2020-10-29 Unilever Plc Systèmes tensioactifs
WO2020216706A1 (fr) * 2019-04-23 2020-10-29 Unilever Plc Systèmes tensioactifs liquides
WO2020216707A1 (fr) * 2019-04-23 2020-10-29 Unilever Plc Systèmes tensioactifs
CN113692439A (zh) * 2019-04-23 2021-11-23 联合利华知识产权控股有限公司 表面活性剂体系
US11814605B2 (en) 2019-04-23 2023-11-14 Conopco Inc. Surfactant systems

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AU4738997A (en) 1998-04-17
AR010228A1 (es) 2000-06-07
MA24330A1 (fr) 1998-04-01
WO1998013455A1 (fr) 1998-04-02
BR9713474A (pt) 2000-04-11
ZA978677B (en) 1998-03-26
CA2267338A1 (fr) 1998-04-02
PL332646A1 (en) 1999-09-27
JP2000503066A (ja) 2000-03-14

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