WO1997003161A9 - Procede pour laver du linge - Google Patents

Procede pour laver du linge

Info

Publication number
WO1997003161A9
WO1997003161A9 PCT/US1996/011282 US9611282W WO9703161A9 WO 1997003161 A9 WO1997003161 A9 WO 1997003161A9 US 9611282 W US9611282 W US 9611282W WO 9703161 A9 WO9703161 A9 WO 9703161A9
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
alkyl
detergent
group
acid
Prior art date
Application number
PCT/US1996/011282
Other languages
English (en)
Other versions
WO1997003161A1 (fr
Inventor
Gerard Marcel Baillely
Robin Gibson Hall
Christian Leo Marie Vermote
Original Assignee
Procter & Gamble
Gerard Marcel Baillely
Robin Gibson Hall
Christian Leo Marie Vermote
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 & Gamble, Gerard Marcel Baillely, Robin Gibson Hall, Christian Leo Marie Vermote filed Critical Procter & Gamble
Priority to EP96923641A priority Critical patent/EP0843714A4/fr
Priority to MX9800274A priority patent/MX9800274A/es
Priority to BR9609600A priority patent/BR9609600A/pt
Publication of WO1997003161A1 publication Critical patent/WO1997003161A1/fr
Publication of WO1997003161A9 publication Critical patent/WO1997003161A9/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents

Definitions

  • This invention relates to a method of washing laundry in a domestic or industrial washing machine, and more especially to such a method wherein a detergent composition containing a cationic ester surfactant is delivered directly to the soiled fabrics in the early stages of the wash.
  • EP-B-21,491 discloses detergent compositions containing a nonionic/cationic surfactant mixture and a builder mixture comprising aluminosilicate and poly carboxy late builder.
  • the cationic surfactant may be a cationic ester. Improved particulate and greasy /oily soil removal is described.
  • US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.
  • US-A-4,239,660 discloses laundry detergent compositions containing cationic ester surfactant and nonionic surfactant at defined weight ratios and an alkalinity source.
  • the alkalinity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minutes of dissolution of the composition in water at 100°F (37°C) at a solution concentration of 0.15%.
  • US-A-4,260,529 discloses laundry detergent compositions having a pH of no greater than 11 containing cationic ester surfactant and nonionic surfactant at defined weight ratios.
  • Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic ester surfactant component.
  • the Applicants have now found that a solution to this problem may be achieved if the cationic surfactant is delivered directly to the soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics by an appropriately designed delivery means.
  • the delivery means may, in a preferred execution, comprise a dispensing device enabling delivery of detergent directly to the soiled fabrics via a dispensing aperture.
  • Dispensing devices in the form of flexible containers, such as bags or pouches but having no distinct dispensing aperture are known in the art, but are not suitable for use in the laundry method of the current invention.
  • the containers are typically made from water-insoluble, but water- permeable material. Dispensing of the detergent product occurs as wash water permeates the container thereby dissolving the contained detergent product which can then pass as a solution into the wash through the container walls.
  • Such containers are not suitable herein in that the surfactant components have a tendency to gel inside the container and thus to be dispensed more slowly, as opposed to simple alkaline salt components which dissolve rapidly and thus dispense rapidly. An alkaline wash environment is thus established prior to the release of the cationic ester surfactants.
  • laundry detergent dispensing means in the form of detergent impregnated fabric sheets are known in the art, but are also not suitable for use in the laundry method of the current invention.
  • Such sheets are typically made from water-insoluble, but water-permeable material. Dispensing of the detergent product occurs as wash water contacts the sheet thereby dissolving the impregnated detergent product which is then released as a solution into the wash.
  • Dispensing means is that the impregnated fabric sheets tend to get enfolded or trapped with the soiled laundry in the wash which hampers dispensing.
  • the surfactant components again have a tendency to gel and thus form a gelatinous surface on the fabric sheet which delays dispensing, as opposed to any simple alkaline salt components which dissolve rapidly and thus dispense rapidly. This again leads to alkaline wash environment being established prior to the release of any cationic ester surfactants.
  • Applicants have also found an alternative but related solution to the problem of decrease in stain removal performance as a result of cationic ester alkaline hydrolysis in the wash.
  • Direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics may also be achieved by appropriate pretreatment of the fabrics with a detergent containing the cationic ester surfactant.
  • the soiled fabrics are pretreated prior to their introduction into the washing machine with a liquid detergent composition formulated to a relatively low pH (i.e. pH ⁇ 9) and containing alkaline components having effect only during the wash.
  • the soiled fabrics are pretreated with a detergent composition containing cationic ester surfactant but no alkaline components.
  • a second detergent composition including alkaline components may then be employed in the wash cycle.
  • said delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of a hydrolysing alkaline wash liquor environment around the soiled laundry.
  • the cationic ester surfactant is selected from those having the formula:
  • Ri is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M".
  • X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R2, R3, R4, R , R7, and Rs are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of
  • a method of washing soiled laundry having a pretreat step comprising application of an effective amount of a detergent composition directly to the soiled laundry before subjecting the soiled laundry to a washing step wherein said detergent composition contains
  • detergent composition from 10% to 99.9% of the detergent composition of detergent components selected from additional surfactants, bleaches, builders, alkalinity sources, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition aag ⁇ eennttss aanndd ccoorrrroossiioonn iinnhhiibbiittoorrss
  • pretreat step enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.
  • 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 defined laundry detergent composition.
  • an effective amount of the detergent composition it is typically meant from 20g to 300g of product dissolved or dispersed in a wash solution of volume from 3 to 65 litres, as are common product dosages and wash solution volumes commonly employed in conventional machine laundry methods. In practice, dosage will alter in accordance with the size of the laundry load and degree of soiling.
  • a delivery means is employed in the washing method of the invention to directly deliver an effective amount of detergent product to the drum of ⁇ e washing machine before commencement of the wash cycle and to enable release of the detergent product into the wash liquor, particularly during the early stages of the wash, more particularly during the first two minutes of the wash.
  • the delivery means enables the delivery of cationic ester surfactant to the soiled laundry prior to the establishment of a hydrolysing alkaline wash liquor environment around the soiled laundry.
  • hydrolysing alkaline wash liquor environment herein it is meant a wash liquor environment that is sufficiently and sustainedly alkaline as to cause significant and rapid hydrolysis of the ester linkage of the cationic ester surfactant, such that its surfactant capability is reduced.
  • this means a pH environment of greater than 9, particularly greater than 10. Higher temperatures can also serve to promote the hydrolysis reaction.
  • said delivery means is a dispensing device having a defined dispensing aperture, particularly one of cross-sectional area greater than 5 cm ⁇ , preferably greater than 7 cm ⁇ .
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method without having to compress the product in the device, which would reduce its release rate.
  • the dispensing device containing the detergent product is placed inside the drum on top of the laundry load, and preferably adjacent to the most soiled areas of the fabrics in the laundry load.
  • water is introduced into the drum and the drum periodically rotates.
  • the detergent product is dispensed from the dispensing aperture and thus is delivered directly to the soiled laundry.
  • the device may possess more than one dispensing aperture through which the product may be dispensed in response to its agitation in the rotating drum.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient lpcalised 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 in accord with 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 Manufacturing 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 in accord with the invention is disclosed in PCT Patent Application No. WO 94/11562.
  • European Patent Application Publication Nos. 0343069 & 0343070 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 and to allow for its dispensing during the early stages of the wash cycle.
  • 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 delivery means is provided by compacting a detergent composition containing both cationic ester and alkaline components into a tablet formed such as to provide release of cationic ester surfactant to the soiled laundry prior to the full release of any alkaline components.
  • the tablets are then introduced directly to the drum of the washing machine prior to commencement of the wash cycle.
  • the tablet comprises layers of distinct product composition with the cationic ester surfactant, being present in a layer outwardly located relative to the layer comprising the alkalinity system, and preferably fully separated from that layer.
  • the direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishment of a hydrolysing alkaline environment around the fabrics may also be achieved by pretreatment of the fabrics with a detergent composition containing the cationic ester surfactant.
  • pretreatment herein means the direct application of a pretreatment detergent composition to a soiled fabric prior to subjecting the soiled fabric to a washing step.
  • the pretreatment composition is generally fluid in nature, that is a solution, liquid, gel, foam or mousse.
  • Application may be achieved by any suitable means including pouring the fluid pretreat composition on the fabric possibly using a suitable dosing means, spray application of a mousse or foam, or applying the fluid using an applicator means such as a sponge or a brush.
  • the pretreatment composition is then manually rubbed into the soiled fabric.
  • the pretreat composition is allowed to remain in contact with the soiled fabric for an effective time interval prior to subjecting the pretreated fabric to the washing step. Said time interval will typically be from 10 seconds to 1800 seconds, more preferably from 60 seconds to 600 seconds.
  • the subsequent washing step is preferably carried out using a washing machine.
  • the soiled fabrics are pretreated with a liquid detergent composition formulated to a relatively low pH, that is pH less than 9.5, more preferably less than 9, most preferably less than 8, but containing alkaline components capable of providing alkalinity during the wash.
  • the alkaline components may for example be coated with a substance which remains intact during the pretreatment step but is removed, e.g. by abrasion, during the washing step.
  • the soiled fabrics are pretreated with a detergent composition containing cationic ester surfactant but no alkaline components.
  • a second detergent composition including alkaline components may then be employed in the wash cycle.
  • the first essential element of the detergent compositions of the invention is a cationic ester surfactant. That is, a preferably water dispersible compound having surfactant properties comprising at least one ester (ie - COO-) linkage and at least one cationically charged group.
  • the cationic ester surfactant is present in amount from 0.1 % to 90%, preferably from 0.5% to 40%, most preferably from 1 % to 30% by weight of the detergent composition.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • Preferred water dispersible cationic ester surfactants are those having the formula:
  • R ⁇ is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M".
  • X and Y independently, are selected from the group consisiting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R2, R3, R4, R6, R7, and Rs are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of
  • R2, 3 and R4 are independently selected from CH3 and -CH2CH2OH.
  • M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula:
  • R is a C11-C19 linear or branched alkyl chain.
  • choline ester compounds among the above disclosed are cocoyl choline ester quaternary methylammonium halides.
  • the particularly preferred choline esters may be prepared h.y the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2- haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.
  • Suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.
  • the cationic ester surfactant is hydrolysable under the conditions of a laundry wash method.
  • the second essential 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 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 mixtures thereof are dissolved in water.
  • Alkali metal percarbonate and persilicate salts are also suitable sources of alkalinity species.
  • carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Alkali metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the section 'inorganic perhydrate salts' herein.
  • Sodium hydroxide is a preferred alkali metal hydroxide herein.
  • Suitable silicates include the water soluble sodium silicates with an Si ⁇ 2: Na2 ⁇ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an Si ⁇ 2: Na2 ⁇ ratio of 2.0 is the most preferred silicate.
  • Alkali metal persilicates are also suitable sources of silicate herein.
  • Preferred crystalline layered silicates for use herein have the general formula
  • NaMSi x ⁇ 2 ⁇ + i.yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na2S-2 ⁇ 5, available from Hoechst AG as NaSKS-6.
  • the crystalline layered silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • the detergent compositions of the invention also contain additional detergent components at a level of from 10% to 99% by weight.
  • 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 contain one or more additional detergent components selected from additional surfactants, bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • the detergent compositions of the invention preferably contain an additional surfactant selected from anionic, nonionic, non-ester cationic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • the additional surfactant is preferably present 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.
  • a preferred component of the detergent compositions is an anionic surfactant.
  • the weight ratio of anionic surfactant to cationic ester surfactant in the surfactant system is preferably from 3:1 to 15:1, more preferably from 4:1 to 12:1, most preferably from 5:1 to 10:1.
  • 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.
  • Suitable 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 saturated and unsaturated C ⁇ -C j g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated ⁇ -C ⁇ diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactant include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates,
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ C4 alkyl) and -N-(Ci-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-CI8 *0cyl sulfates, more preferably the C11-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C11-C18, most preferably C11-C15 alkyl 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 sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • 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 olefin sulfonates, sulfonated poly carboxy lie acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Anionic carboxylate surfactant 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 C ⁇ to Ci8 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 to Ci8 alkyl group, x is from 1 to 25, Ri and 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures 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- 1-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 sarcosinates of formula R-CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R* is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R* is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Alkoxylated nonionic surfactant Essentially 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 ethoxylated/propoxylated fatty alcohols, nonionic ethoxy late/propoxy late 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 structural formula R ⁇ CONR ⁇ Z 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 Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture 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
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R6C0N(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.
  • Nonionic alkylpolysaccharide surfactant 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
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures 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.
  • 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 R3(OR4) X N U (R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ 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 C ⁇ o _ Cl8 alkyl dimethylamine oxide, and Cj ⁇ -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+R 2 COO- wherein R is a hydrocarbyl group, each R* is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the CiO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C16, preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxy ethyl or hydroxypropyl groups.
  • the detergent compositions of the present invention preferably contain a 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 polycarboxylates, 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 mixtures 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, gly colic 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 tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • 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 hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
  • 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 present invention may 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 Na z [(Al ⁇ 2) z (Si ⁇ 2)y]. 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
  • Zeolite X has the formula Na 8 6 [(AlO 2 )86(SiO 2 )l06]. 276 H 2 0.
  • a preferred feature 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 mixtures 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 mixtures 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 incorporated 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 substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -SO ⁇ ' M , -C ⁇ 2 ⁇ M , -SO ⁇ ' M , -N + (R 3 ) X " and 0 ⁇ -N(R 3 ) 3 and most preferably -S0 3 " M + and -C ⁇ 2 ⁇ M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, 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 substituted 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 nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursors are suitable herein, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R 2 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 substituted 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 substituted and unsubstituted 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 substituted 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 substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted 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; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted 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 j 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 substituted compounds of the following general formulae: R 1 — C — N — R 2 — C — OOH R 1 — N — C — R 2 — C — OOH
  • Rl 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 substituted 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.
  • 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 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, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • ethylenediaminetetraacetic acid ethylenediaminetetra(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
  • 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 (IV) 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.
  • binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands including N4Mni ⁇ (u-0)2MnrVN4)+and [Bipy2Mn ⁇ i( u -0)2MnI bipy2]-(Cl ⁇ 4)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.
  • 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.
  • 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-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypro ⁇ yl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-509,382 The ⁇ - alanine-N,N'-diacetic acid, aspartic acid-N,N' -diacetic acid, aspartic acid- N-monoacetic acid and iminodisuccinic acid sequestrants described in EP- A-509,382 are also suitable.
  • 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 alos suitable.
  • Glycinamide-N,N'-disuccinic acid Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
  • Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • 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 Opticiean and Optimase by Solvay Enzymes.
  • 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 and BAN by Novo Industries A/S.
  • 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., Thermomyces 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 Humicola lanuginosa and expressing the gene in Aspergillus oryza ⁇ as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • 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.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • 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 mixtures 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 alkanolammomum salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-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 C ⁇ - Ci 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 mixture 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.
  • the detergent compositions herein 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 : P
  • A is NC, CO, C, -0-, -S-, -N-; x is 0 or1;
  • 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-O group is part of these groups.
  • the N-0 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.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O 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-0 functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-0 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 vailable from ISP Corporation, 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 Corporation.
  • 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 structural formula:
  • Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxy ethyl, N-2- hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ 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 Corporation. 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 Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino- 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 Corporation.
  • Cationic fabric softening agents can also be incorporated 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 Oil 340.
  • Cationic fabric softening agents are typically incorporated 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 and tablet forms.
  • the compositions are particularly the so-called concentrated 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.
  • the term 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 500 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.
  • Tablet forms are generally made by compressing granular compositions into tablet shape using any of the tabletting process commonly known in the art.
  • the hardness of the tablet may be varied.
  • the size of the tablets is selected to enable ease of dosing to the wash solution.
  • a tablet will comprise from 5 to lOOg, preferably from 10 to 50g of detergent product.
  • the tablet may be of essentially any shape including cubes and spheres.
  • the tablet is formed such as to have at least two distinct and separate layers, wherein an outer layer contains cationic ester surfactant and an inner layer the alkalinity system.
  • the surfactant system herein is preferably present in granular compositions in the form of surfactant 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 surfactant 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 surfactant 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 manufactured 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 surfactant 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 manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse
  • a high active surfactant 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 anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
  • Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
  • Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
  • C25E3 A C 12- 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide
  • Nai2(A102Si ⁇ 2)l2- 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
  • Silicate Amorphous Sodium Silicate Si ⁇ 2:Na2 ⁇ ; 2.0 ratio
  • MA/AA Copolymer of 1:4 maleic/acrylic acid average molecular weight about 70,000.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .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 Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
  • laundry detergent compositions A to F were prepared in accord with the invention:
  • compositions A to AA of Sets 1 to 8 were employed in a laundry washing method in which a Miele 820 automatic washing machine was employed, and the 40°C short cycle programme selected.
  • lOOg of detergent was placed in a granulette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) detergent products, as made by the Procter and Gamble Company, for sale across Europe.
  • the charged granulette was then placed on top of the wash load in the drum of the washing machine.
  • the wash load comprised 2.4Kg of 60/40 mixture of lightly soiled cotton, polycotton and polyester fabrics. Good washing performance was obtained.
  • the sets of fabric swatches were subjected to one wash cycle in an automatic washing machine with the detergent dispensed either from a granulette or from the dispensing drawer of the washing machine.
  • the swatches were then assessed for removal of the various fatty stains by a four person grading panel using the well-known four-point Scheffe scale.
  • the detergent was placed in a granulette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) detergent products, as made by the Procter and Gamble Company, for sale across Europe.
  • Ariel trademark
  • the charged granulette was then placed on top of the ballast wash load and adjacent to the stained swatches in the drum of the washing machine and the wash cycle started.
  • Each of the detergent products AB to Al was used separately in a pretreatment washing method involving the following steps:
  • a load of 2 Kg of soiled polycotton and cotton fabrics was taken.
  • approximately 5ml aliquots of detergent product were applied directly to fatty soiled areas, until the area was at least wetted with the detergent.
  • the detergent was allowed to remain in contact with the soiled area for 5 minutes.
  • the wash step the load was then placed in a Miele 820 automatic washing and the 40°C short cycle programme selected. 100ml of the same detergent product was employed in the wash cycle.
  • the detergent was dispensed from a solid plastic dosing ball. Good washing performance was obtained for each of products AB to A

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

Abstract

L'invention concerne un procédé pour laver du linge sale dans une machine à laver domestique ou industrielle, où un distributeur est prévu pour envoyer une dose efficace de composition détergente directement dans le tambour de la machine à laver avant le commencement du lavage et pour permettre une libération subséquente du détergent dans la liqueur de lavage durant le lavage. La composition détergente contient un tensioactif cationique du type ester et un système apportant de l'alcalinité, constitué de sels alcalins. Le distributeur permet d'envoyer le tensioactif cationique du type ester au linge sale avant la constitution d'un environnement comprenant la liqueur de lavage alcaline autour du linge sale. L'invention concerne également un procédé de lavage comprenant une étape de prélavage.
PCT/US1996/011282 1995-07-08 1996-07-03 Procede pour laver du linge WO1997003161A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96923641A EP0843714A4 (fr) 1995-07-08 1996-07-03 Procede pour laver du linge
MX9800274A MX9800274A (es) 1995-07-08 1996-07-03 Metodo de lavado de ropa.
BR9609600A BR9609600A (pt) 1995-07-08 1996-07-03 Processo de lavagem em lavanderia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9513991.1 1995-07-08
GB9513991A GB2303150A (en) 1995-07-08 1995-07-08 Laundry washing method

Publications (2)

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WO1997003161A1 WO1997003161A1 (fr) 1997-01-30
WO1997003161A9 true WO1997003161A9 (fr) 1999-06-24

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BR (1) BR9609600A (fr)
CA (1) CA2226637A1 (fr)
GB (1) GB2303150A (fr)
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WO (1) WO1997003161A1 (fr)

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US8533881B2 (en) 2009-12-15 2013-09-17 Whirpool Corporation Method for dispensing an enzyme in a laundry treating appliance
US10005850B2 (en) 2013-12-16 2018-06-26 E I Du Pont De Nemours And Company Use of poly alpha-1,3-glucan ethers as viscosity modifiers
CN106029700B (zh) 2013-12-18 2019-04-12 纳幕尔杜邦公司 阳离子聚α-1，3-葡聚糖醚
CN105992796A (zh) 2014-02-14 2016-10-05 纳幕尔杜邦公司 用于粘度调节的聚-α-1,3-1,6-葡聚糖
JP2017515921A (ja) 2014-03-11 2017-06-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 酸化されたポリα−１，３−グルカン
US9714403B2 (en) 2014-06-19 2017-07-25 E I Du Pont De Nemours And Company Compositions containing one or more poly alpha-1,3-glucan ether compounds
EP3919599A1 (fr) 2014-06-19 2021-12-08 Nutrition & Biosciences USA 4, Inc. Compositions contenant un ou plusieurs composés d'éther de poly alpha-1,3-glucane
EP3277730B1 (fr) 2015-04-03 2022-02-09 Nutrition & Biosciences USA 4, Inc. Éthers de dextrane gélifiants
US9890350B2 (en) 2015-10-28 2018-02-13 Ecolab Usa Inc. Methods of using a soil release polymer in a neutral or low alkaline prewash
US10876074B2 (en) 2015-11-13 2020-12-29 Dupont Industrial Biosciences Usa, Llc Glucan fiber compositions for use in laundry care and fabric care
JP7045313B2 (ja) 2015-11-13 2022-03-31 ニュートリション・アンド・バイオサイエンシーズ・ユーエスエー・フォー，インコーポレイテッド 洗濯ケアおよび織物ケアにおいて使用するためのグルカン繊維組成物
JP2019504932A (ja) 2015-11-13 2019-02-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 洗濯ケアおよび織物ケアにおいて使用するためのグルカン繊維組成物
WO2019118674A1 (fr) 2017-12-14 2019-06-20 E. I. Du Pont De Nemours And Company Copolymères greffés d'alpha-1,3-glucane
CN113574074B (zh) 2018-10-25 2023-03-21 营养与生物科学美国第四公司 α-1,3-葡聚糖接枝共聚物
EP4100446A1 (fr) 2020-02-04 2022-12-14 Nutrition & Biosciences USA 4, Inc. Dispersions aqueuses d'alpha-glucane insoluble comprenant des liaisons glycosidiques alpha-1,3
BR112022024705A2 (pt) 2020-06-04 2023-02-28 Nutrition & Biosciences Usa 4 Inc Composição, método para produzir um composto de éter ou éster de copolímero de enxerto, método de floculação e método de absorção
EP4294849A1 (fr) 2021-02-19 2023-12-27 Nutrition & Biosciences USA 4, Inc. Dérivés de polysaccharide pour compositions détergentes
EP4334363A1 (fr) 2021-05-04 2024-03-13 Nutrition & Biosciences USA 4, Inc. Compositions comprenant un alpha-glucane insoluble
EP4370560A1 (fr) 2021-07-13 2024-05-22 Nutrition & Biosciences USA 4, Inc. Dérivés d'ester de glucane cationique
WO2023081346A1 (fr) 2021-11-05 2023-05-11 Nutrition & Biosciences USA 4, Inc. Dérivés de glucane pour la lutte antimicrobienne
WO2023114942A1 (fr) 2021-12-16 2023-06-22 Nutrition & Biosciences USA 4, Inc. Compositions comprenant des éthers d'alpha-glucane cationiques dans des solvants organiques polaires aqueux
WO2024015769A1 (fr) 2022-07-11 2024-01-18 Nutrition & Biosciences USA 4, Inc. Dérivés amphiphiles d'ester de glucane
WO2024081773A1 (fr) 2022-10-14 2024-04-18 Nutrition & Biosciences USA 4, Inc. Compositions comprenant de l'eau, un éther d'alpha-1,6-glucane cationique et un solvant organique

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MX9800274A (es) 1998-04-30
EP0843714A4 (fr) 2000-01-05
GB9513991D0 (en) 1995-09-06
WO1997003161A1 (fr) 1997-01-30
EP0843714A1 (fr) 1998-05-27
BR9609600A (pt) 1999-05-04
CA2226637A1 (fr) 1997-01-30
GB2303150A (en) 1997-02-12

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