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WO2000066704A1 - Microspheres utiles dans des compositions detergentes - Google Patents

Microspheres utiles dans des compositions detergentes Download PDF

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Publication number
WO2000066704A1
WO2000066704A1 PCT/US2000/011306 US0011306W WO0066704A1 WO 2000066704 A1 WO2000066704 A1 WO 2000066704A1 US 0011306 W US0011306 W US 0011306W WO 0066704 A1 WO0066704 A1 WO 0066704A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
acid
compositions
agents
surfactants
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.)
Ceased
Application number
PCT/US2000/011306
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English (en)
Inventor
Walter August Maria Broeckx
James Pyott Johnston
Jean-Pol Boutique
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
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AU44945/00A priority Critical patent/AU4494500A/en
Publication of WO2000066704A1 publication Critical patent/WO2000066704A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • This invention relates to detergent compositions, more particularly laundry detergent compositions and/or products, such as heavy duty aqueous and/or non-aqueous and/or gelled liquid laundry detergents and granular and/or powder laundry detergents, which include one or more microspheres having a polymeric expandable outer shell made of a polymeric mate ⁇ al that is soluble in an alkaline aqueous solution, wherein the shell defines a cavity containing a means for expanding the microsphere such that the microsphere cavity's volume increases.
  • the microspheres of the present invention can be used as low density filler particles and/or encapsulates comp ⁇ smg one or more detergent ingredients.
  • non-aqueous heavy duty liquid detergents which comp ⁇ se a surfactant system in a non-aqueous organic solvent combined with particulate solids which have beneficial effects in the wash (e g , bleaches and bleach activators), have a tendency to be quite unstable and thus, result in the sedimentation and/or settling out of the particulate solids as well as the formation of a clear liquid layer at the surface of the product.
  • EP 839 902 discloses a process for the production of microspheres containing a bleach aid for use in detergents.
  • this reference fails to teach microspheres in the form of low density filler particles and/or encapsulates comp ⁇ smg one or more detergent ingredients wherein the microspheres comp ⁇ se an expandable outer shell that defines a cavity containing a means for expanding the microsphere.
  • this reference fails to teach the use of water soluble and/or easily dispersible m water low density filler particles for improving the physical stability and the dissolution of laundry detergents, especially non-aqueous liquid laundry detergents
  • the present invention fulfills the needs identified above by providing detergent compositions, preferably laundry detergent compositions and/or products compnsmg one or more microspheres preferably in the form of low density fillers and/or encapsulates compnsmg one or more detergent ingredients.
  • the microspheres of the present invention compnse a polymenc expandable outer shell made of a polymenc matenal that is soluble in an alkaline aqueous solution and wherein the shell defines a cavity containing a means for expanding the microsphere such that the microsphere cavity's volume increases.
  • Detergent compositions preferably laundry detergent compositions and/or products, more preferably liquid laundry detergent compositions and/or products employing the microspheres of the present invention exhibit properties such that the tendency of particulate solids and/or encapsulates within the laundry detergent to sediment and/or settle out of the laundry detergent is reduced.
  • the microspheres of the present invention preferably in the form of low density fillers and/or encapsulates compnsmg one or more detergent ingredients into laundry detergent compositions and/or products, especially non- aqueous liquid laundry detergents, that contain detergent ingredients in the form of particulate solids and/or encapsulates compnsmg one or more detergent ingredients, the particulate solids and/or encapsulate can be stably suspended in liquid laundry detergent products.
  • the particulate solids and/or encapsulates withm the laundry detergent products of the present invention have a reduced tendency to sediment and/or settle out of the laundry detergent products dunng storage and/or transportation.
  • particulate solids and/or encapsulates compnsmg one or more detergent ingredients having a reduced tendency to sediment and/or settle out of the laundry detergent products
  • consumers can have more comstent doses with respect to the level of actives, especially the particulate solids, per dose.
  • particulate solids and/or encapsulates compnsmg one or more detergent ingredients having a reduced tendency to sediment and/or settle out of the laundry detergent products, the appearance of a clear top layer in the product is inhibited and/or resisted.
  • the dissolution of the product is not impaired as the microspheres of the present invention maintain a low product viscosity.
  • the microspheres of the present invention which are either water soluble or easily dispersible in water, the microspheres do not result m unacceptable residues on fabncs and on washing machine parts dunng use.
  • the present invention provides a way to suspend heavy solids in a laundry detergent, preferably a non-aqueous liquid laundry detergent without increasing the low shear viscosity of the detergent, thus avoiding any slow down of the rate of dissolution in the wash which may occur as a result of increasing the low shear viscosity of the detergent.
  • a laundry detergent preferably a non-aqueous liquid laundry detergent
  • the mileage of the product is not reduced as a result of product hang-up in the bottle.
  • a microsphere comp ⁇ smg a polymenc expandable outer shell made of a polymenc material that is soluble in an alkaline aqueous solution and wherein the shell defines a cavity containing a mean-T for expanding the microsphere such that the microsphere cavity's volume increases is provided.
  • the microsphere is m the form of a low density filler particle which is useful m stably suspending detergent ingredients in the form of particulate solids in laundry detergent compositions, especially in liquid laundry detergent compositions.
  • the microsphere is in the form of encapsulates containing one or more detergent ingredients which are useful in stably suspending the detergent ingredients withm the encapsulates in laundry detergent compositions, especially in liquid laundry detergent compositions.
  • a method for making a microsphere having a polymeric expandable outer shell made of a polymenc matenal that is soluble in an alkaline aqueous solution and wherein the shell defines a cavity containing a means for expanding the " microsphere such that the microsphere cavity's volume increases is provided.
  • a detergent composition preferably a laundry detergent composition and/or product compnsmg one or more microspheres having a polymenc expandable outer shell made of a polymenc mate ⁇ al that is soluble m an alkaline aqueous solution and wherein the shell defines a cavity containing a means for expanding the microsphere such that the microsphere cavity's volume increases, and one or more cleaning adjunct mate ⁇ als in the form of particulate solids is provided.
  • a liquid laundry detergent composition compnsmg one or more microspheres having a polymenc expandable outer shell made of a polymenc mate ⁇ al that is soluble m an alkaline aqueous solution and wherein the shell defines a cavity containing a means for expanding the microsphere such that the microsphere cavity's volume increases, and one or more cleaning adjunct matenals in the form of particulate solids is provided.
  • a granular and/or powder laundry detergent product compnsmg one or more microspheres having a polymenc expandable outer shell made of a polymenc matenal that is soluble in an alkaline aqueous solution and wherein the shell defines a cavity containing a means for expanding the microsphere such that the microsphere cavity's volume increases, and one or more cleaning adjunct matenals m the form of particulate solids is provided.
  • a method for making the microspheres of the present invention is provided.
  • a method for launde ⁇ ng fabncs comprising contacting the fabrics with the laundry detergent compositions and/or products of the present invention, preferably the liquid laundry detergent composition and/or product of the present invention, is provided.
  • a method for stabilizing a liquid laundry detergent composition comprising particulate solids wherein the method comp ⁇ ses the step of adding one or more microspheres of the present invention to the composition is provided.
  • a method for inhibiting the formation of a clear top layer m a liquid laundry detergent composition compnsmg particulate solids wherein the method compnses the step of adding one or more microspheres of the present invention to the composition is provided.
  • a method for reducing and/or preventing the deposit of residues on a fabnc in need of laundenng dunng laundenng of the fabnc with a liquid laundry detergent composition compnsmg particulate solids wherein the method comp ⁇ ses the step of adding one or more microspheres of the present invention to the composition is provided.
  • FIG. 1 is a schematic representation of the microspheres in accordance with the present invention.
  • FIG. 2 is a schematic representation of the microsphere of FIG. 1 after expansion.
  • the present invention relates to detergent compositions, more particularly laundry detergent compositions and/or products that compnse one or more microspheres m the form of low density fillers and/or encapsulates compnsmg one or more detergent ingredients wherein the microspheres compnse an expandable outer shell that defines a cavity containing a means for expanding the microspheres and wherein the laundry detergent compositions and/or products exhibit properties such that the tendency of the particulate solids withm the laundry detergent and/or encapsulates to sediment and/or settle out of liquid laundry detergent products is reduced and methods of making such laundry detergent compositions and/or products.
  • Low Density Filler Particles herein is meant any component that when incorporated into a laundry detergent composition and or product compnsmg particulate solids exhibits a reduced tendency for the particulate solids to sediment and/or settle out of the laundry detergent composition and/or product.
  • Suitable examples of low density filler particles include, but are not limited to, water soluble or water insoluble organic or inorganic matenals, microspheres (liquid hydrocarbon-containing and/or gas-contammg depending upon temperature, and/or hollow) and other components that result a reduction of the tendency of the particulate solids withm a laundry detergent composition and/or product to sediment and/or settle out of the laundry detergent composition and or product.
  • the low density filler particles of the present invention are water soluble and/or easily dispersible in water.
  • Porate solids herein is meant any detergent mgredient/cleamng adjunct mate ⁇ al that is in the form of a solid (i.e., granules, powder, flakes, chips, particles, etc.). Preferably, the particulate solids have a particle size of from 1-2000 microns.
  • Encapsulates herein is meant any the microspheres of the present invention that comp ⁇ se one or more detergent ingredients within the cavity of the microsphere.
  • the microspheres of the present invention are particularly useful m laundry detergent compositions, more particularly liquid laundry detergent compositions. However, such microspheres may be in other types of cleaning compositions, especially liquid cleaning compositions such as liquid dishwashing compositions and liquid hard surface cleaning compositions.
  • the microspheres of the present invention are particularly useful in laundry detergent compositions m the form of low density filler particles, wherein the low density filler particles have a tendency to stabilize and/or resist the sedimentation and/or settling out of the detergent ingredients with the compositions that are in the form of particulate solids by suspending such particulate solids.
  • the laundry detergent compositions of the present invention preferably the liquid laundry detergent compositions of the present invention, more preferably the non-aqueous liquid laundry detergent compositions of the present invention include the low density filler particles and particulate solids at levels such that the ratio of the average particle size diameter of the low density filler particles to the average particle size diameter of the dispersed particulate solids is preferably less than 6: 1, more preferably less than 5:1, even more preferably less than 4: 1, still even more preferably less than 3: 1, yet even more preferably less than 2: 1, most preferably about 1 : 1.
  • the microspheres of the present invention are particularly useful in laundry detergent compositions in the form of encapsulates which contain one or more detergent ingredients, which are typically in the form of particulate solids.
  • Such encapsulates have a tendency to stabilize and/or resist the sedimentation and/or settling out of the detergent ingredients with the compositions that are in the form of particulate solids by suspending such particulate solids.
  • Polymeric Expandable Outer Shell As shown in FIGs. 1 and 2, the polymenc expandable outer shell 12, 12' of the microsphere 10, 10' of the present invention is made of a polymenc mate ⁇ al that is soluble in alkaline aqueous solutions.
  • the polymenc matenal of the polymenc expandable outer shell 12, 12' comp ⁇ ses as an essential ingredient an anhyd ⁇ de.
  • the anhyd ⁇ de is selected from the group consisting of: ethylenically unsaturated monocarboxy c acid anhydndes; ethylemcally unsaturated dicarboxy c acid anhydndes and mixtures thereof.
  • the polymenc matenal of the polymenc expandable outer shell 12, 12' can further comp ⁇ se additional monomenc mate ⁇ als.
  • additional monome ⁇ c matenals include, but are not limited to, monoethylemcally unsaturated monomers which differ from the ethylenically unsaturated carboxylic acid anhydndes and which do not react with the anhydndes; cross-linking agents (monomers which have a cross linking action and have at least two monoethylemcally unsaturated, non-conjugated double bindings); polar, water-soluble monoethylemcally unsaturated monomers and mixtures thereof.
  • the anhydnde and one or more additional monome ⁇ c matenals preferably comp ⁇ se 100% by weight of the polymenc matenal compnsmg the polymenc expandable outer shell.
  • blowing agents that are soluble in the anhyd ⁇ de and/or the additional monome ⁇ c mate ⁇ als compnsmg the polymenc matenal may also be included in the polymenc expandable outer shell 12, 12' as a result of the process for making the microspheres 10, 10' of the present invention.
  • the anhyd ⁇ de and one or more additional monome ⁇ c materials may be present m the polymeric material at any weight ratio, provided that the polymenc mate ⁇ al comprises anhydride and that the polymeric mate ⁇ al is soluble in alkaline aqueous solutions.
  • the anhydndes preferably ethylenically unsaturated carboxylic acid anhydndes include both monocarboxyhc acid anhydndes and dicarboxyhc acid anhydndes.
  • Preferred ethylenically unsaturated carboxylic acid anhydndes of the present invention preferably include from about 2 to about 20, more preferably from about 3 to about 12, most preferably from about 3 to about 6 carbon atoms.
  • Suitable ethylenically unsaturated monocarboxyhc acid anhydndes include, but are not limited to, monocarboyxlic acids selected from the group consisting of: acrylic acid; methacrylic acid; ethylacryhc acid; allylacetic acid; crotomc acid; v ylacetic acid and mixtures thereof.
  • the ethylenically unsaturated monocarboxyhc acid anhydndes are selected from the group consisting of acrylic acid anhydnde; methacrylic acid anhyd ⁇ de and mixtures thereof.
  • Ethylenically unsaturated monocarboxyhc acid anhydndes which have two ethylemc double bonds permit cross-lmking within the polymenc matenal of the polymenc expandable outer shell, when they are used. Such ethylenically unsaturated monocarboxyhc acid anhydndes thus can also act as cross-lmking agents.
  • Suitable ethylenically unsaturated dicarboxyhc acid anhydndes include, but are not limited to, dicarboxyhc acids selected from the group consisting of: maleic acid; C ⁇ -C ⁇ 2, preferably Cj-Cg mono- and/or dialkyl maleic acid; maleic acid monoaklyester; ltacomc acid; mesaconic acid; fumanc acid; citracomc acid; methylenemalonic acid; acomtic acid and mixtures thereof.
  • the ethylenically unsaturated dicarboxyhc acid anhydndes are selected from the group consisting of maleic acid anhydnde; ltacomc acid anhydnde; citracomc acid anhydnde and mixtures thereof.
  • the ethylenically unsaturated dicarboxyhc acid anhydndes are ethylenically unsaturated inner dicarboxyhc acid anhydndes.
  • the ethylenically unsaturated inner dicarboxyhc acid anhydndes can be incorporated into the polymenc matenal of the polymenc expandable outer shell without having any cross-linking in the polymenc matenal.
  • ethylenically unsaturated monocarboxyhc acid anhydndes preferably acrylic acid anhydnde
  • ethylenically unsaturated dicarboxyhc acid anhydndes preferably maleic acid anhydnde
  • the weight ratio of said ethylenically unsaturated dicarboxyhc acid anhydndes, preferably maleic acid anhyd ⁇ de, to said ethylenically unsaturated monocarboxyhc acid anhydndes, preferably acrylic acid anhydride is from about 1 :10 to about 10.1, more preferably from about 1 :5 to about 5: 1
  • the ethylenically unsaturated carboxylic acid anhydndes of the present invention are preferably present m the polymenc material compnsmg the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention at a level of from about 5% to about
  • Suitable monoethylemcally unsaturated monomers which differ from the ethylenically unsaturated carboxylic acid anhydndes and which do not react with the anhydndes include, but are not limited to, acrylic acid and/or methacrylic acid esters of monovalent Ci -C24 alcohols.
  • Preferred monoethylemcally unsaturated monomers of this type include, but are not limited to, methyl acrylate, methylmethacrylate, ethylacrylate, ethylmethacrylate, n-propylacrylate, n- propylmethacrylate, isopropylacrylate, lsopropylmethacrylate, n-butylacrylate, isobutylacrylate, t- butyl acrylate, n-butylmethacrylate, isobutylmethacrylate, t-butyl methacrylate, octylacrylate, octylmethacrylate, 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, laurylacrylate, laurylmethacrylate, stearylacrylate, palmitylacrylate, stearylmethacrylate, palmitylmethacrylate, styrol, ⁇
  • More preferred monoethylemcally unsaturated monomers of this type are selected from the group consisting of: methyl acrylate, methylmethacrylate, ethylacrylate, ethylmethacrylate, styrol, vinyl acetate, v ylpy ⁇ dine and mixtures thereof.
  • the monoethylemcally unsaturated monomers which differ from the ethylenically unsaturated carboxylic acid anhydndes and which do not react with the anhydndes of the present invention are preferably present m the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention at a level of from about 0% to about 95%, more preferably from about 0% to about 90% by weight of the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12'
  • Suitable cross-linking agents include, but are not limited to, acrylic acid and methacrylic acid esters which are denved from alcohols which contain bivalent alcohols containing from about 2 to about 24 carbon atoms and mixtures thereof.
  • Preferred monomers of this type include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1 ,4-butand ⁇ ol diacrylate, 1 ,4-butand ⁇ ol dimethacrylate, 1.6-hexand ⁇ ol diacrylate, 1,6-hexand ⁇ ol dimethacrylate, divinylbenzol, methallylmethacryloamide, allylmethacrylate, allylacrylate, methylenebisacryloamide, tnmethylolpropane tnacrylate, tnmethylolpropane tnmethacrylate, pentaerythntol tnallylether, pentaerythntol tetraacrylate, pentaerythntol tetramethacrylate and mixtures thereof.
  • cross-linking agents preferably permit the polymenc expandable outer shell 12, 12' to swell and become more permeable in alkaline aqueous solutions without permitting the polymenc expandable outer shell 12, 12' to dissolve completely or burst.
  • the permeability of the polymenc expandable outer shell 12, 12' is desired, especially m the case of the microspheres 10, 10' of the present invention which contain one or more detergent ingredients within its cavity 14, 14', in order to release the matenals contained within the microsphere's cavity 14, 14' at an uncontrolled and/or spontaneous rate or a controlled (delayed) rate.
  • the rate of release of matenals contained withm the cavity 14, 14' of the microspheres 10, 10' of the present invention is dependent upon the amount and type of cross-linking agents present m the polme ⁇ c mate ⁇ al compnsmg the polymenc expandable outer shell 12, 12*.
  • the cross-linking agents of the present invention tngger a delayed release of the contents of the cavity 14, 14' of the microspheres 10, 10' of the present invention, which may possibly be dissolved m oil, after the hydrolysis of the polymenc mate ⁇ al compnsmg the polymenc expandable outer shell 12, 12'.
  • cross-linking agents of the present invention are preferably present m the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention at a level of from about 0% to about 80%, more preferably from about 0% to about 50% by weight of the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12'.
  • the cross-linking agents do not react with the anhydndes, discussed above, dunng the polymenzation process for the polymenc mate ⁇ al.
  • Suitable polar, water-soluble monoethyle cally unsaturated monomers including, but not limited to, acrylic acid, methacrylic acid, acrylamide, hydroxyethylacrylate, hydroxyethylmethacrylate, vmylsulfomc acid, acrylamidopropanesulfomc acid, styrolsulfonic acid, sulfoethylacrylate, sulfoethylmethacrylate, sulfopropylacrylate, sulfopropylmethacrylate, acrylonitnle and mixtures thereof.
  • the polar, water-soluble monoethylemcally unsaturated monomers are selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, hydroxyethylacrylate, hydroxyethylmethacrylate, vinylsulfomc acid, acrylamidopropanesulfonic acid, styrolsulfonic acid, sulfoethylacrylate, sulfoethylmethacrylate, sulfopropylacrylate, sulfopropylmethacrylate and mixtures thereof
  • the polar, water-soluble monoethylemcally unsaturated monomers of the present invention are preferably present in the polymenc matenal compnsmg the expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention at a level of from about 0% to about 20%, more preferably from about 0% to about 10% by weight of the polymenc matenal comprising the polymenc expandable outer shell 12, 12'.
  • the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention preferably compnse, in addition to the anhyd ⁇ de, one or more of the additional monome ⁇ c mate ⁇ als desc ⁇ bed above. Additional or further descnptions of the anhydndes and/or additional monome ⁇ c mate ⁇ als for use m the polymenc matenal of the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention are desc ⁇ bed in EP 839 902 published May 6, 1998 in the name of BASF.
  • the anhyd ⁇ de and preferably one or more additional monome ⁇ c matenals of the polymenc matenal comprising the polymenc expandable outer shell 12, 12' are preferably selected such that the expanded microspheres 10', as represented in FIG. 2, of the present invention have a density of less than 0.4 g/mL; more preferably less than 0.2 g/mL; most preferably less than 0.1 g/mL.
  • the polymenc matenal of the polymenc expandable outer shell 12, 12' can be and preferably is designed such that the microspheres 10, 10' of the present invention can substantially, preferably completely withm 5 minutes, preferably withm 3 minutes, more preferably withm 1 minute of coming into contact with an alkaline aqueous solution.
  • the amount and types of mate ⁇ als compnsmg the polymenc mate ⁇ al of the polymenc expandable outer shell 12, 12' influences the dissolution rate of the microspheres 10, 10' of the present invention.
  • the polymenc matenal of the polymenc expandable outer shell 12, 12' can be designed such that the microspheres of the present invention dissolve such that contents withm the microspheres 10, 10', such as softening agents, enzymes and other detergent ingredients partially or fully incompatible with an alkaline aqueous solution are released from the microspheres 10, 10' in a delayed and/or controlled manner.
  • the partially or fully incompatible detergent ingredients do not enter the alkaline aqueous solution all at once, but over a penod of time
  • the ethylenically unsaturated dicarboxyhc acid anhydndes such as maleic acid anhydride have a slower hydrolysis than the ethylenically unsaturated monocarboxhc acid anhydndes, such as -acrylic acid anhydnde.
  • the rate of hydrolysis of the ethylenically unsaturated dicarboxyhc acid anhydndes results in the polymenc material compnsmg the polymeric expandable outer shell 12, 12' to swell.
  • the ethylenically unsaturated monocarboxyhc acid anhydndes result m the disruption of cross-linking agents, and thus result in the polymenc matenal compnsmg the polymeric expandable outer shell 12, 12' to dissolve, rather than swell. Accordingly, the ratio of ethylenically unsaturated monocarboxyhc acid anhydndes to ethylenically unsaturated dicarboxyhc acid anhydndes in the polymenc material compnsmg the polymenc expandable outer shell 12, 12' controls the rate of dissolution of the outer shell 12 and thus the release of the contents of the microsphere's cavity 14, 14'. Blowing Agents
  • microspheres 10, 10' of the present invention contain withm their cavity 14, 14' formed and/or defined by their polymenc expandable outer shell 12, 12' a means for expanding the microspheres.
  • the means for expanding the microsphere are capable of increasing the microsphere cavity's volume.
  • a preferred means for expanding the microsphere of the present invention such that the microsphere cavity's volume increases include, but are not limited to, blowing agents contained withm the cavity 14, 14' of the microspheres 10, 10' of the present invention and/or heating the microspheres 10, 10' of the present invention .
  • Suitable blowing agents for use in the microspheres 10, 10' of the present invention include, but are not limited to, the blowing agents desc ⁇ bed in U.S. Patent No. 3,615,972 issued October 26, 1971 m the name of The Dow Chemical Company.
  • blowing agents include, but are not limited to, aliphatic hydrocarbons, chlorofluorocarbons, nitrogen, carbon dioxide, oxygen, tetraalkyl silanes and mixtures thereof.
  • blowing agents are selected from the group consisting of aliphatic hydrocarbons.
  • Preferred aliphatic hydrocarbons include, but are not limited to, ethane, ethylene, propane, propene, butene, isobutene, isobutane, neopentane, isopentane, acetylene, hexane, heptane, propylene, n-butane, n-pentane, petroleum ether, halogemzed methane, and mixtures thereof.
  • Suitable tertraalkyl silanes include, but are not limited to, tetramethyl silane, tnmethylethyl silane, tnmethyhsopropyl silane and tnmethyl n-propyl silane. It is desirable that the boiling point of such blowing agents at atmosphe ⁇ c pressure is about the same temperature range or lower than the softening point of the anhydnde and additional monomenc matenals, when present, -of the polymenc matenal compnsmg the polymenc expandable outer shell 12, 12' of the microspheres 10, 10' of the present invention. Cavity Contents
  • one or more detergent ingredients may be contained within the cavity 14, 14' of the microspheres 10, 10' of the present invention. It is highly preferred to incorporate the detergent ingredients, especially when they are in the form of particulate solids, into the cavity 14, 14' of the microspheres 10, 10' of the present invention when the microspheres 10, 10' are used m liquid laundry detergents. By placing the particulate solid detergent ingredients withm the cavity 14, 14' of the microspheres 10, 10', the tendency of the particulate solid detergent ingredients to sediment and/or settle out of the liquid laundry detergent is reduced.
  • Suitable detergent ingredients for incorporation into the cavity 14, 14' of the microspheres 10, 10' of the present invention include but are not limited to, surfactants, builders, bleaching agents, dye transfer inhibiting agents, chelants, dispersants, polysacchandes, ohgosaccha ⁇ des, softening agents, suds suppressors, earners, enzymes, enzyme stabilizing systems, polyacids, soil removal agents, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bactencides, dyes, perfumes, b ⁇ ghteners, anti-encrustation agents and mixtures thereof.
  • Preferred detergent ingredients are selected from the group consisting of: surfactants, builders, bleaching agents, chelants, enzymes, soil removal agents, anti-redeposition agents, perfumes and mixtures thereof.
  • the microspheres 10, 10' of the present invention are preferably made by any suitable process known in the art.
  • the microspheres 10, 10' are made by a suspension polymenzation of droplets of a mixture of expandable outer shell mate ⁇ als and one or more of blowing agents and detergent ingredients, as more fully desc ⁇ bed in EP 839 902 published May 6, 1998 in the name of BASF and/or U.S. Patent Nos. 3,615,972, 4,108,806, 4,075,138, 4,016,110, 3,945,956, 4,075,134 and 4,049,604 all in the name of The Dow Chemical Company.
  • the microspheres 10, 10' of the present invention are readily prepared from a wide va ⁇ ety of matenals.
  • the microspheres 10, 10' are typically prepared by providing an aqueous dispersion and/or suspension comprising: a) one or more anhydndes and preferably one or more additional monomenc mate ⁇ als preferably suitable for polymerization to form the polymenc mate ⁇ al comprising the polymeric expandable outer shell of the microspheres of the present invention having the desired physical properties desc ⁇ bed herein, b) a blowing agent which preferably exerts little solvent action on the resulting polymenc expandable outer shell of the microspheres of the present invention and is either insoluble in the polymeric expandable outer shell or is in a quantity in excess of that which is soluble m the polymenc expandable outer shell; and c) a dispersion stabilizing matenal, preferably one or more protective colloids, which preferably is utilized to maintain the dispersion, subsequently polymenzing the anhydndes and preferably one or more additional monomenc mate ⁇ als to form the polymenc matenal compnsmg the poly
  • Suspensions of the anhydnde and additional monomenc mate ⁇ als for the preparation of the polymenc matenal compnsmg the polymenc expandable outer shell of the microspheres 10, 10' of the present invention are typically made employing one or more dispersion stabilizing mate ⁇ als, preferably protective colloids.
  • the polymenzation is initiated by a suitable catalyst, preferably, an oil-soluble catalyst, which is incorporated into the aqueous dispersion.
  • Suitable catalysts include, but are not limited to, peroxide compounds, such as organic peroxides, as well as radiation, such as high energy ionizing radiation.
  • Suitable organic peroxides include, but are not limited to, benzyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl perbenzoate, cumene hydroperoxide, cumene ethylperoxide and mixtures thereof
  • the method for making the microspheres 10, 10' of the present invention is preferably earned out an oxygen-free environment and in the absence of free radical chain-terminating matenals. Such an environment can easily be accomplished by flushing the aqueous dispersion system with an inert atmosphere such as nitrogen.
  • the anhyd ⁇ de and additional monome ⁇ c mate ⁇ als and blowing agents constitute a major portion of the oil phase withm the aqueous dispersion, and are incorporated with water m a ratio of from about 1 : 1 oil-phase to water to about 1 6 oil-phase to water.
  • the dispersion stabizing mate ⁇ al is incorporated within the water phase and the expandable outer shell matenals, blowing agents and catalyst are mixed, preferably dunng violent agitation if the microspheres 10, 10' are desired to have a smaller diameter.
  • the diameter of the droplets of polymenzable aqueous dispersion, and hence the diameter of the polymenc expandable outer shell microspheres of the present invention, can be va ⁇ ed predictably, by deliberate vanation of the composition of the aqueous dispersion, withm the range of from about one-half of a micron or less to about 0.5 centimeter.
  • the diameter of the droplets formed by the process range from about 1 micron to about 100 microns, " more preferably from about 1 micron to about 50 microns.
  • the polymenzation method for making the microspheres 10, 10' is typically earned out at a temperature of from about 20 °C to about 90 °C, more preferably from about 40 °C to about 65 °C.
  • the preferred method for making the microspheres 10, 10' of the present invention compnses dispersing one part by volume of a mixture of one or more anhydndes and preferably one or more additional monomenc mate ⁇ als and one or more blowing agents into at least 0.5, preferably from about 0.5 to bout 10 or more parts by volume of a nonsolvent aqueous medium compnsmg water and: a) a water-dispersible, water-insoluble protective colloid, the particles of which, in aqueous dispersion, have dimensions in the order of from about 0.008 to about 50 microns, which particles tend to gather at the liquid-liquid interface or are caused to do so by the presence of one or more of the following optional ingredients: i) a water-soluble "promoter" that affects the "hydrophihc- hydrophobic balance" of the protective colloids; and/or n) an electrolyte such as alkali metal and ammonium salts; and/or in) colloid-active modifiers such as pe
  • Suitable dispersion stabilizing materials include, but are not limited to, protective colloids.
  • Preferred protective colloids are cellulose denvatives, polyvmylpyrrolidone, copolymers of N-vmyl pyrrohdone, polyvmyl alcohol and partially hydrolyzed polyvmyl acetates.
  • Preferred cellulose denvatives are selected from the group consisting of: carboxymethylcellulose (CMC), ethylhydroxyethylcellulose (EHEC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxybutylcellulose (HBC), methylcellulose (MC), ethylcellulose (EC), propylcellulose (PC), carboxymethylhydroxyethylcellulose (CMHEC), methoxypropyl methyl cellulose (MPMC), hexylcarboxymethyl cellulose, C12 - C20 alkyl carboxymethylcellulose, methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), hydroxybutylmethylcellulose (HBMC) and mixtures thereof.
  • CMC carboxymethylcellulose
  • EHEC ethylhydroxyethylcellulose
  • HPC hydroxypropylcellulose
  • HBC hydroxybutylcellulose
  • cellulose denvatives are commercially available from the following companies: Aqualon, Dow Chemical, ShimEtsu, MetsaSeila, Akzo Nobel, Zoltak, Nippon Soda, Sigma.
  • HPMC Hydroxypropyl-cellulose
  • HPMC Hydroxypropylmethylcellulose
  • CMC Carboxymethylcellulose
  • MC Methylcellulose
  • Metolose SM from ShmEtsu Chemical Co.,Ltd, Benecel from Aqualon
  • Methylhydroxyethylcellulose (HEMC) e.g. Metolose SE from Shin Etsu Chemical Co., Ltd
  • Hydroxyethylcellulose (HEC)- Natrosol from Aqualon Carbomethylhydroxyethylcellulose
  • Ethylhydroxyethylcellulose Aqualon from Aqualon.
  • Additional protective colloids that are suitable for use in the present invention include, but are not limited to, gelatine, gum arable, xanthan, sodium algmate, pectin, partly hydrolyzed starch and casein.
  • Protective colloids are used alone or in the form of mixtures of protective colloids.
  • protective colloids are used m accordance with the present invention at levels of from about 0.1% to about 10%, preferably from about 0.5% to about 5% by weight of the mixture of the dispersion stabilizing material, preferably protective colloid, and one or more expandable outer shell mate ⁇ als.
  • LAUNDRY COMPOSITIONS are used m accordance with the present invention at levels of from about 0.1% to about 10%, preferably from about 0.5% to about 5% by weight of the mixture of the dispersion stabilizing material, preferably protective colloid, and one or more expandable outer shell mate ⁇ als.
  • the laundry compositions of the present invention preferably also compnse, m addition to one or more microspheres 10, 10' of the present invention and one or more particulate solids of the present invention descnbed hereinbefore, one or more cleaning adjunct mate ⁇ als, preferably compatible with the microspheres 10, 10' and the detergent ingredient particulate sohd(s).
  • cleaning adjunct matenals means any liquid, solid or gaseous mate ⁇ al selected for the particular type of laundry composition desired and the form of the product (e.g., liquid; granule; powder; gel composition), which matenals are also preferably compatible with the microspheres 10, 10' of the present invention.
  • cleaning adjunct matenals are readily made by considenng the surface, item or fabric to be cleaned, and the desired form of the composition for the laundry conditions dunng use (e.g., through the wash detergent use).
  • compatible means the cleaning adjunct matenals do not reduce the detersive activity of the non- enzyme detergent ingredients in the particulate solids to such an extent that the non-enzyme detergent ingredients are not effective as desired dunng normal use situations.
  • cleaning adjunct matenals include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical bnghteners, soil release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabnc conditioners, hydrolyzable surfactants, perservatives, anti-oxidants, anti-shnnkage agents, anti-wnnkle agents, germicides, fungicides, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubi zmg agents, earners, processing aids, pigments and pH control agents as descnbed in U.S.
  • Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101 Specific cleaning adjunct matenals are exemplified m detail hereinafter. If the cleaning adjunct matenals are not compatible with the microspheres and the detergent ingredient particulate solids withm the laundry compositions, then suitable methods of keeping the cleaning adjunct matenals separate from (not in contact with each other) the microspheres and the detergent ingredient particulate solids until combination of the cleaning adjunct matenals and the microspheres and detergent ingredient particulate solids is appropnate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc.
  • compositions useful for laundenng a vanety of fabncs m need of cleaning Preferably an effective amount of one or more particulate solids descnbed above are included in compositions useful for laundenng a vanety of fabncs m need of cleaning.
  • effective amount of one or more particulate solids refers to the quantity of particulate solids of the present invention descnbed hereinbefore necessary to achieve the detersive activity necessary m the specific laundry composition. Such effective amounts are readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular enzyme used, the laundry application, the specific composition of the laundry composition, and whether a liquid or dry (e.g., granular, powder) composition is required, and the like.
  • laundry detergent compositions of the present invention compnse:
  • a laundry detergent composition of the present invention comp ⁇ ses one or more microspheres of the present invention and one or more particulate solids of the present invention such that the density difference between the density of the laundry detergent composition and/or product and the density of the particulate solids is equivalent to the density difference seen m a laundry detergent composition and/or product wherein the density difference between the density of a laundry detergent composition and/or product and the density of a particulate solid is less than about 0.2 g/mL, more preferably less than about 0.1 g/mL, most preferably less than about 0.05 g mL.
  • the laundry detergent compositions and/or products of the present invention comp ⁇ se from about 0.001%, preferably from about 0.1%, more preferably from about 0.25% by weight of the laundry compositions of one or more particulate solids of the present invention, to about 50%, preferably to about 25%, more preferably to about 10%.
  • the laundry compositions comp ⁇ se from about 0 1%, preferably from about 1%, more preferably from about 2%, by weight of the laundry compositions of one or more particulate solids of the present invention, to about 60%, preferably to about 40%, more preferably to about 25% Several examples of various laundry compositions wherein the particulate solids of the present invention may be employed are discussed in further detail below Also, the laundry compositions may include from about 1% to about 99 9% by weight of the composition of the cleaning adjunct matenals.
  • fabric laundry compositions include hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabncs
  • the compositions of the present invention preferably contain both a surfactant and a builder compound and additionally one or more cleaning adjunct matenals preferably selected from organic polymenc compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Laundry compositions can also contain softening agents, as additional cleaning adjunct mate ⁇ als.
  • compositions of the present invention can also be used as detergent additive products m solid or liquid form.
  • Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the laundry process.
  • the density of the laundry detergent compositions herein ranges from 400 to 1200 g/htre, preferably 500 to 950 g/htre of composition measured at 20°C.
  • the "compact" form of the laundry compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts are selected from the alkali and alkaline-earth-metal salts of sulfates and chlondes.
  • a preferred filler salt is sodium sulfate
  • Liquid laundry compositions according to the present invention can also be m a "concentrated form", in such case, the liquid laundry compositions according the present invention will contain a lower amount of water, .compared to conventional liquid detergents Typically the water content of the concentrated liquid laundry composition is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the laundry composition.
  • the laundry detergent compositions and/or products preferably incorporate microspheres of the present invention m an amount sufficient to suspend the particulate solids of the present invention such that the laundry detergent compositions and/or products of the present invention are similar in properties to laundry detergent compositions and/or products compnsmg particulate solids having a particle density of from about 0.8 to about 2.1 g/mL, more preferably from about 0.8 to about 1.5 g/mL, most preferably from about 0.9 to about 1.2 g/mL.
  • Non-aqueous, liquid, heavy-duty detergent compositions in accordance with the present invention are in the form of a stable suspension of solid, substantially insoluble particulate matenal dispersed throughout a structured, surfactant-containing liquid phase.
  • Such detergent compositions comp ⁇ se from about 49% to 99.95% by weight of the composition of a structured, surfactant-containing liquid phase formed by combining: i) from about 1% to 80% by weight of said liquid phase of one or more nonaqueous organic diluents; and n) from about 20% to 99% by weight of said liquid phase of a surfactant system compnsmg surfactants selected from the group consisting of anionic, noniomc, cationic surfactants and combinations thereof.
  • the surfactant-containing, non-aqueous liquid phase of the non-aqueous liquid laundry detergent compositions of the present invention will generally compnse from about 52% to about 98.9% by weight of the detergent compositions herein. More preferably, this liquid phase is surfactant-structured and will compnse from about 55% to 98% by weight of the compositions. Most preferably, this non-aqueous liquid phase will comp ⁇ se from about 55% to 70% by weight of the compositions herein. Such a surfactant-containing liquid phase will frequently have a density of from about 0.6 to 1.4 g/cc, more preferably from about 0.9 to 1.3 g/cc.
  • the liquid phase of the detergent compositions herein is preferably formed from one or more non-aqueous organic diluents into which is mixed a surfactant structuring agent which is preferably a specific type of aniomc surfactant-containing powder l Non-aqueous Organic Diluents
  • the major component of the liquid phase of the detergent compositions herein comp ⁇ ses one or more non-aqueous organic diluents
  • the non-aqueous organic diluents used in this invention may be either surface active, i.e., surfactant, liquids or non-aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
  • surface active i.e., surfactant, liquids or non-aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
  • solvent is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions herein.
  • compositions herein may actually dissolve m the "solvent"-conta ⁇ n ⁇ ng liquid phase, other components will be present as particulate matenal dispersed within the "solvent"-contammg liquid phase.
  • solvent is not meant to require that the solvent mate ⁇ al be capable of actually dissolving all of the detergent composition components added thereto.
  • the non-aqueous liquid diluent component will generally comp ⁇ se from about 50% to 100%), more preferably from about 50% to 80%, most preferably from about 55%> to 75%, of a structured, surfactant-containing liquid phase.
  • the liquid phase of the compositions herein, i.e., the non-aqueous liquid diluent component will comp ⁇ se both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents. u.
  • Non-aqueous Surfactant Liquids Suitable types of non-aqueous surfactant liquids which can be used to form the liquid phase of the compositions herein include the alkoxylated alcohols, ethylene oxide (EO)- propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkylpolysaccha ⁇ des, and the like. Such normally liquid surfactants are those having an HLB ranging from 10 to 16. Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are matenals which correspond to the general formula:
  • R 1 (C m H 2m O) n OH wherein R 1 is a Cg - C j g alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R 1 is an alkyl group, which may be pnmary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated mate ⁇ als that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol mate ⁇ als useful m the liquid phase will frequently have a hydrophihc-hpophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophihc-hpophilic balance
  • fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms m its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated p ⁇ mary Cj2 - Cj3 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C11 pnmary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C9-C1 ⁇ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C ⁇ -C ⁇ fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15- S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C1 j to C ⁇ linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Neodol 45-11 are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
  • alcohol alkoxylate noniomc surfactant is utilized as part of the non-aqueous liquid phase in the detergent compositions herein, it will preferably be present to the extent of from about 1% to 60% of the composition structured liquid phase. More preferably, the alcohol alkoxylate component will comp ⁇ se about 5% to 40% of the structured liquid phase. Most preferably, an alcohol alkoxylate component will comp ⁇ se from about 5% to 35% of the detergent composition structured liquid phase. Utilization of alcohol alkoxylate in these concentrations m the liquid phase corresponds to an alcohol alkoxylate concentration in the total O 00/66704
  • composition of from about 1% to 60% by weight, more preferably from about 2% to 40% by weight, and most preferably from about 5% to 25% by weight, of the composition.
  • Non-aqueous surfactant liquid which may be utilized m this invention are the ethylene oxide (EO) - propylene oxide (PO) block polymers.
  • Materials of this type are well known noniomc surfactants which have been marketed under the tradename Pluronic These matenals are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
  • Pluronic ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
  • EO-PO block polymer noniomcs of this type are desc ⁇ bed m greater detail in Davidsohn and Milwidsky; Synthetic Detergents. 7th Ed : Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S.
  • non-aqueous surfactant liquid useful m the compositions herein compnses polyhydroxy fatty acid amide surfactants. If present, the polyhydroxy fatty acid amide surfactants are preferably present in a concentration of from about 0.1 to about 8%. Matenals of this type of noniomc surfactant are those which conform to the formula:
  • R— C— N— Z wherein R is a Cg. ⁇ j alkyl or alkenyl, p is from 1 to 6, and Z is glycityl denved from a reduced sugar or alkoxylated denvative thereof.
  • mate ⁇ als include the C ⁇ -Cjg N-methyl glucamides Examples are N-methyl N-1-deoxygluc ⁇ tyl cocoamide and N-methyl N-l- deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid, amides are know and can be found, for example, in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S.
  • Patent 2,703,798 the disclosures of which are incorporated herein by reference.
  • the matenals themselves and their preparation are also descnbed in greater detail in Honsa, U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also incorporated herein by reference.
  • the amount of total liquid surfactant in the preferred surfactant-structured, non-aqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
  • the liquid surfactant can compnse from about 35% to 70% of the non-aqueous liquid phase of the compositions herein. More preferably, the liquid surfactant will compnse from about 50% to 65% of a non-aqueous structured liquid phase. This corresponds to a non-aqueous liquid surfactant concentration in the total composition O 00/66704
  • Non-surfactant Non-aqueous Organic Solvents of from about 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition.
  • the liquid phase of the detergent compositions herein may also comprise one or more non-surfactant, non-aqueous organic solvents.
  • non-surfactant non-aqueous liquids are preferably those of low polanty.
  • low-polanty liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate mate ⁇ al used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol are preferably not utilized.
  • Matenals of this type include hexylene glycol (4-methyl-2,4-pentaned ⁇ ol), 1 ,6-hexaned ⁇ ol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.
  • non-aqueous, low-polanty solvent for use herein compnses the mono-, di-, t ⁇ -, or terra- C2-C3 alkylene glycol mono -C alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are especially preferred.
  • PEGs polyethylene glycols
  • non-polar, non-aqueous solvent compnses lower molecular weight methyl esters.
  • Such matenals are those of the general formula: R 1 -C(0)-OCH3 wherein
  • R! ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the non-aqueous, generally low-polanty, non-surfactant organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e g , bleach and/or activators, used m the liquid detergent compositions herein
  • a solvent component is preferably utilized in an amount of from about 1% to 70% by weight of the liquid phase
  • a non-aqueous, low-polanty, non-surfactant solvent will comp ⁇ se from about 10% to 60% by weight of a structured liquid phase, most preferably from about 20% to 50% by weight, of a structured liquid phase of the composition
  • Utilization of non-surfactant solvent m these concentrations in the liquid phase corresponds to a non-surfactant solvent concentration in the total composition of from about 1 % to 50% by weight, more preferably from about 5% to 40% by weight, and most preferably from about 10% to 30% by weight, of the composition.
  • the ratio of surfactant to non-surfactant liquids e.g., the ratio of alcohol alkoxylate to low polanty solvent, withm a structured, surfactant-containing liquid phase can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of surfactant liquid to non-surfactant organic solvent will range about 50: 1 to 1:50. More preferably, this ratio will range from about 3:1 to 1 :3, most preferably from about 2:1 to 1 :2.
  • the non-aqueous liquid phase of the detergent compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents hereinbefore desc ⁇ bed a surfactant which is generally, but not necessa ⁇ ly, selected to add structure to the non-aqueous liquid phase of the detergent compositions herein.
  • Structu ⁇ ng surfactants can be of the anionic, noniomc, cationic, and/or amphote ⁇ c types.
  • Preferred structunng surfactants are the anionic surfactants such as the alkyl sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates.
  • anionic surfactant matenal which may be optionally added to the detergent compositions herein as structurant compnses carboxylate-type aniomcs
  • Carboxylate-type anionics include the C JQ- Cjg alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C JQ- I S sarcosmates, especially oleoyl sarcosmate
  • Yet another common type of anionic surfactant matenal which may be employed as a structurant comprises other sulfonated anionic surfactants such as the Cg-Cjg paraffin sulfonates and the Cg-Cjg olefin sulfonates Structunng ani
  • one preferred type of structuring anionic surfactant comp ⁇ ses pnmary or secondary alkyl sulfate anionic surfactants.
  • Such surfactants are those produced by the sulfation of higher C -C20 fatty alcohols.
  • R0S0 3 -M + wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubihzmg cation.
  • R is a C JO- 14 alkyl, and M is alkali metal.
  • R is about C ⁇ 2 and M is sodium.
  • Conventional secondary alkyl sulfates may also be utilized as a structunng anionic surfactant for the liquid phase of the compositions herein.
  • Conventional secondary alkyl sulfate surfactants are those matenals which have the sulfate moiety dist ⁇ ubbed randomly along the hydrocarbyl "backbone" of the molecule. Such matenals may be depicted by the structure: CH 3 (CH 2 )n(CH0S03-M + ) (CH 2 ) m CH 3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 15, and
  • M is a water-solubihzmg cation.
  • alkyl sulfates will generally compnse from about 1% to 30% by weight of the composition, more preferably from about 5% to 25%> by weight of the composition.
  • Non-aqueous liquid detergent compositions containing alkyl sulfates, peroxygen bleaching agents, and bleach activators are descnbed in greater detail in Kong-Chan et al.; WO 96/10073; Pubhched Apnl 4,
  • mate ⁇ al which may be optionally added to the non-aqueous laundry compositions herein as a structurant comp ⁇ ses the alkyl polyalkoxylate sulfates.
  • Alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates.
  • Such mate ⁇ als are those which correspond to the formula
  • R ⁇ IS a C10- 22 alky- group, m is from 2 to 4, n is from about 1 to 15, and M is a salt- forming cation.
  • R ⁇ is a C ⁇ - j g alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium.
  • R ⁇ is a Cl2"Cl6> m is 2, n is from about 1 to 6, and M is sodium.
  • Ammonium, alkylammonium and alkanolammonium counte ⁇ ons are preferably avoided when used in the compositions herein because of incompatibility with peroxygen bleaching agents.
  • alkyl polyalkoxylate sulfates can also generally comp ⁇ se from about 1% to
  • Non-aqueous liquid detergent compositions containing alkyl polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides, are desc ⁇ bed in greater detail in boutique et al; PCT Application No PCT/US96/04223, which application is incorporated herein by reference.
  • anionic surfactant for use as a structurant m the compositions herein comp ⁇ ses the linear alkyl benzene sulfonate (LAS) surfactants.
  • LAS surfactants can be formulated into a specific type of anionic surfactant-contammg powder which is especially useful for incorporation into the non-aqueous liquid detergent compositions of the present invention.
  • Such a powder comp ⁇ ses two distinct phases. One of these phases is insoluble in the non-aqueous organic liquid diluents used m the compositions herein; the other phase is soluble in the non-aqueous organic liquids.
  • this preferred anionic surfactant-contammg powder which can be dispersed in the non-aqueous liquid phase of the preferred compositions herein and which forms a network of aggregated small particles that allows the final product to stably suspend other solid particulate matenals m the composition.
  • Such a preferred anionic surfactant-contammg powder is formed by co-drying an aqueous slurry which essentially contains a) one of more alkali metal salts of C JQ-16 linear alkyl benzene sulfomc acids; and b) one or more non-surfactant diluent salts.
  • a slurry is dned to a solid mate ⁇ al, generally in powder form, which comp ⁇ ses both the soluble and insoluble phases.
  • the linear alkyl benzene sulfonate (LAS) mate ⁇ als used to form the preferred anionic surfactant-contammg powder are well known matenals.
  • Such surfactants and their preparation are descnbed for example in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference.
  • the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14
  • Sodium C ⁇ ⁇ - ⁇ , e.g., C ⁇ , LAS is especially preferred.
  • the alkyl benzene surfactant anionic surfactants are generally used m the powder-formmg slurry in an amount from about 20 to 70% by weight of the slurry, more preferably from about 20% to 60% by weight of the slurry.
  • the powder-formmg slurry also contains a non-surfactant, organic or inorganic salt component that is co-d ⁇ ed with the LAS to form the two-phase anionic surfactant-contammg powder.
  • a non-surfactant, organic or inorganic salt component that is co-d ⁇ ed with the LAS to form the two-phase anionic surfactant-contammg powder.
  • Such salts can be any of the known sodium, potassium or magnesium hahdes, sulfates, citrates, carbonates, sulfates, borates, succmates, sulfo-succmates and the like.
  • Sodium sulfate which is generally a bi-product of LAS production, is the preferred non-surfactant diluent salt for use herein.
  • Salts which function as hydrotropes such as sodium sulfo-succinate may also usefully be included
  • the non-surfactant salts are generally used m the aqueous slurry, along with the LAS, m amounts ranging from about 1 to 50% by weight of the slurry, more preferably from about 5% to 40% by weight of the slurry. Salts that act as hydrotropes can preferably comp ⁇ se up to about 3% by weight of the slurry.
  • the aqueous slurry containing the LAS and diluent salt components hereinbefore descnbed can be dned to form the anionic surfactant-contammg powder preferably added to the non-aqueous diluents m order to prepare a structured liquid phase withm the compositions herein.
  • Any conventional drying technique e.g., spray drying, drum drying, etc., or combination of drying techniques, may be employed. Drying should take place until the residual water content of the solid matenal which forms is within the range of from about 0.5% to 4% by weight, more preferably from about 1% to 3% by weight.
  • the anionic surfactant-contammg powder produced by the drying operation constitutes two distinct phases, one of which is soluble in the inorganic liquid diluents used herein and one of which is insoluble in the diluents.
  • the insoluble phase m the anionic surfactant-contammg powder generally comp ⁇ ses from about 10% to 45% by weight of the powder, more preferably from about 15% to 35% by weight of a powder.
  • the anionic surfactant-containing powder that results after drying can compnse from about 45%o to 94%, more preferably from about 60% to 94%, by weight of the powder of alkyl benzene sulfonic acid salts. Such concentrations are generally sufficient to provide from about 0.5% to 60%, more preferably from about 15% to 60%>, by weight of the total detergent composition that is eventually prepared, of the alkyl benzene sulfonic acid salts.
  • the anionic surfactant-contammg powder itself can compnse from about 0.45% to 45% by weight of the total composition that is eventually prepared. After drying, the anionic surfactant-contammg powder will also generally contain from about 2% to 50%, more preferably from about 2% to 25% by weight of the powder of the non-surfactant salts.
  • the combined LAS/salt mate ⁇ al can be converted to flakes or powder form by any known suitable milling or comminution process.
  • the particle size of this powder will range from 0.1 to 2000 microns, more preferably from about 0.1 to 1000 microns.
  • a structured, surfactant-containing liquid phase of the preferred detergent compositions herein can be prepared by combining the non-aqueous organic diluents hereinbefore desc ⁇ bed with the anionic surfactant-contammg powder as hereinbefore desc ⁇ bed. Such combination results in the formation of a structured surfactant-containing liquid phase. Conditions for making this combination of preferred structured liquid phase components are desc ⁇ bed more fully hereinafter in the "Composition Preparation and Use" section. As previously noted, the formation of a structured, surfactant-contammg liquid phase permits the stable suspension of colored speckles and additional functional particulate solid mate ⁇ als within the preferred detergent compositions of this invention.
  • noniomc surfactants specifically, polyhydroxy fatty acid amides of the formula:
  • R— C — N — Z wherein R is a C9.17 alkyl or alkenyl, R ⁇ is a methyl group and Z is glycityl de ⁇ ved from a reduced sugar or alkoxylated denvative thereof.
  • Examples are N-methyl N-1-deoxygluc ⁇ tyl cocoamide and N-methyl N-1-deoxygluc ⁇ tyl oleamide.
  • Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the disclosures of which are incorporated herein by reference.
  • Preferred surfactants for use in the detergent compositions descnbed herein are amine based surfactants of the general formula:
  • R j is a Cg-C ⁇ alkyl group; n is from about 2 to about 4, X is a bndgmg group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH 2 -0(R5)) wherein R5 is H or methyl.
  • Especially preferred amines based surfactants include the following:
  • Rj is a Cg-C ⁇ alkyl group and R5 is H or CH3.
  • Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octyl amme, hexyl amme, decyl amme, dodecyl amme, Cg-Ci2 b ⁇ s(hydroxyethyl)amme, Cg-C ] 2 b ⁇ s(hydroxy ⁇ sopropyl)amme, C -Ci2 amido-propyl dimethyl amme, or mixtures thereof.
  • amme based surfactant is desc ⁇ bed by the formula R!-C(0)-NH-(CH2)3-N(CH3)2 wherein Rj is C -Cj2 alkyl.
  • non-aqueous detergent compositions herein preferably compnse from about 0.01% to
  • particulate matenal 50% by weight, more preferably from about 0.2% to 30% by weight, of solid phase particulate matenal which is dispersed and suspended withm the liquid phase.
  • particulate matenal will range in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably, such mate ⁇ al will range in size from about 5 to 200 microns.
  • the particulate mate ⁇ al utilized herein can comp ⁇ se one or more types of detergent composition components which in particulate form are substantially insoluble in the non-aqueous liquid phase of the composition.
  • the types of particulate mate ⁇ als which can be utilized are descnbed in detail as follows: AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS SURFACTANTS
  • the present invention also comprises aqueous based liquid detergent compositions.
  • the aqueous liquid detergent compositions preferably compnse from about 10% to about 98%, preferably from about 30% to about 95%, by weight of an aqueous liquid earner which is preferably water
  • the aqueous liquid detergent compositions of the present invention compnse a surfactant system which preferably contains one or more detersive co- surfactants in addition to the branched surfactants disclosed above.
  • the additional co-surfactants can be selected from noniomc detersive surfactant, anionic detersive surfactant, zwittenomc detersive surfactant, amme oxide detersive surfactant, and mixtures thereof
  • the surfactant system typically comp ⁇ ses from about 5% to about 70%, preferably from about 15% to about 30%, by weight of the detergent composition. i. Anionic Surfactant
  • Anionic surfactants include Ci j-Cig alkyl benzene sulfonates (LAS) and primary, branched-cham and random C10-C20 alkyl sulfates (AS), the CjQ-Ci secondary (2,3) alkyl
  • x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubihzmg cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the CJQ- Cjg alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), Cj Q -Cig alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the CjQ.jg glycerol ethers, the CI Q-CJ g alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ⁇ - j alpha-
  • anionic surfactants useful herein are disclosed in U.S. Patent No 4,285,841, Barrat et al, issued August 25, 1981, and m U.S. Patent No. 3,919,678, Laughlm et al, issued December 30, 1975.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or tnethanolammomum) salts, of organic sulfu ⁇ c reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group (Included in the term "alkyl” is the alkyl portion of aryl groups.)
  • alkyl sulfates especially those obtained by sulfatmg the higher alcohols (Cg-C j carbon atoms) such as those produced by reducing the glycendes of tallow or coconut oil.
  • anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of a- sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms m the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms m the alkane moiety.
  • Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula:
  • RO(C 2 H 4 0) x S03-M + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated C 12-15 pnmary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
  • fatty acids include capnc, launc, mynstic, palmitic, stea ⁇ c, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, lmoleic, hnolenic, and ⁇ cmoleic acid.
  • Conventional noniomc and amphote ⁇ c surfactants include C ⁇ -C ⁇ g alkyl ethoxylates
  • AE including the so-called narrow peaked alkyl ethoxylates and -C ⁇ 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy)
  • the CiQ-Cj N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Ci2-C ⁇ N- methylglucamides. See WO 9,206,154.
  • Other sugar-de ⁇ ved surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C JQ-C I S N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C ⁇ -Cig glucamides can be used for low sudsmg.
  • C10-C20 conventional soaps may also be used. If high sudsmg is desired, the branched-cham C10-C16 soaps may be used Examples of noniomc surfactants are descnbed in U S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981 00/66704
  • these surfactants include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC 2 H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms m the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol.
  • Mixtures of anionic and noniomc surfactants are especially useful.
  • Other conventional useful surfactants are listed m standard texts, including C ⁇ 2 -C ⁇ betames and sulfobetames (sultames).
  • Amine Oxide Surfactants The compositions herein also contain amine oxide surfactants of the formula:
  • R' is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R* is a pnmary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R ⁇ is a pnmary alkyl moiety.
  • Ri is a hydrocarbyl moiety having chamlength of from about 8 to about 18.
  • R ⁇ may be somewhat longer, having a chamlength m the range Cj 2 -C 2 4-
  • These amme oxides are illustrated by C ⁇ 2 _i4 alkyldimethyl amme oxide, hexadecyl dimethylarnine oxide, octadecylamme oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R* is a pnmary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; m these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4, EO represents ethyl eneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amme oxide manufacturers.
  • Preferred commercially available amme oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamme oxide dihydrate, octadecyldimethylamme oxide dihydrate, hexadecyltns(ethyleneoxy)d ⁇ methyl-amme oxide, tetradecyldimethylamme oxide dihydrate, and mixtures thereof.
  • R' is H
  • R' is CH 2 OH, such as hexadecylb ⁇ s(2- hydroxyethyl)am ⁇ ne oxide, tallowb ⁇ s(2-hydroxyethyl)amme oxide, stearylb ⁇ s(2-hydroxyethyl)am ⁇ ne oxide and oleylb ⁇ s(2- hydroxyethyl)amme oxide.
  • the present invention encompasses a heavy duty gel laundry detergent compositions compnsmg, by weight of the composition: a) from about 15% to about 40% of an anionic surfactant component which compnses, by weight of the composition:
  • alkyl polyethoxylate sulfates wherein the alkyl group contains from about 10 to about 22 carbon atoms and the polyethoxylate chain contains from 0.5 to about 15, preferably from 0.5 to about 5, more preferably from
  • compositions herein may further contain one or more additional detersive additives selected from the group consisting of non-citrate builders, optical b ⁇ ghteners, soil release polymers, dye transfer inhibitors, polymenc dispersing agents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, antiredeposition agents, antifadmg agent, dye fixative agents, pnll/fuzzing reducing agents, and mixtures thereof.
  • additional detersive additives selected from the group consisting of non-citrate builders, optical b ⁇ ghteners, soil release polymers, dye transfer inhibitors, polymenc dispersing agents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, antiredeposition agents, antifadmg agent, dye fixative agents, pnll/fuzzing reducing agents, and mixtures thereof.
  • compositions herein have a viscosity at 20 s'l shear rate of from about 100 cp to about 4,000 cp, preferably from about 300 cp to about 3,000 cp, more preferably from about 500 cp to about 2,000 cp and are stable upon storage.
  • compositions herein are structured and have a specific rheology.
  • the term "structured” indicates a heavy duty liquid composition having a liquid crystalline lamellar phase and an infinite shear viscosity ( ⁇ o) value between 0 and about 3,000cp (centipoise), a shear index ( «) value of less than about 0.6, a consistency index value, K, of above about 1,000, and a viscosity ( ⁇ ) measured at 20 s" 1 of less, than about 10,000cp, preferably less than about 5,000cp.
  • a “zero shear” viscosity is above about 100,000cp wherein “zero shear” is meant a shear rate of 0.001 s-"* or less.
  • the yield value of the compositions herein is larger than 0.2Pa. These rheology parameters can be measured with any commercially available rheometer, such as the Cammed CSL 100 model.
  • the compositions herein are clear or translucent, i.e. not opaque. Electrolytes - Without being limited by theory, it is believed that the presence of electrolytes acts to control the viscosity of the gel compositions. Thus, the gel nature of the compositions herein are affected by the choice of surfactants and by the amount of electrolytes present.
  • compositions will further compnse from 0% to about 10%, more preferably from about 1% to about 8%, even more preferably from about 2%> to about 6%, of a suitable electrolyte or acid equivalent thereof.
  • Sodium citrate is a highly preferred electrolyte for use herein.
  • compositions herein may optionally contain from about 0% to about 10%, by weight, of solvents and hydrotropes.
  • solvent is meant the commonly used solvents m the detergent industry, including alkyl monoalcohol, di-, and tn-alcohols, ethylene glycol, propylene glycol, propanediol, ethanediol, glycenne, etc.
  • hydrotrope is meant the commonly used hydrotropes in the detergent industry, including short chain surfactants that help solubihze other surfactants.
  • hydrotropes include cumene, xylene, or toluene sulfonate, urea, Cg or shorter chain alkyl carboxylates, and Cg or shorter chain alkyl sulfate and ethoxylated sulfates.
  • Modified polyamme - may comp ⁇ se at least about 0.05%, preferably from about 0.05% to about 3%, by weight, of a water-soluble or dispersible, modified polyamme agent, said agent compnsmg a polyamme backbone corresponding to the formula:
  • each R ⁇ is independently C2-C5 alkylene, alkenylene or arylene; each R 2 is independently H, or a moiety of formula OH[(CH2) x O] n , wherein x is from about 1 to about 8 and n is from about 10 to about 50; w is 0 or 1; x+y+z is from about 5 to about 30; and B represents a continuation of this structure by branching; and wherein said polyamme before alkylation has an average molecular weight of from about 300 to about 1,200.
  • R! IS C2-C4 alkylene, more preferably ethylene;
  • R 2 is
  • n is from about 15 to about 30, more preferably n is about 20.
  • the average Molecular Weight of the polyarmne before alkylation is from about 300 to about 1200, more preferably from about 500 to about 900, still more preferably from about 600 to about 700, even more preferably from about 600 to about 650.
  • R ⁇ is C 2 -C4 alkylene, more preferably ethylene;
  • R 2 is
  • n is from about 10 to about 20, more preferably n is about 15.
  • the average Molecular Weight of the polyarmne before alkylation is from about 100 to about 300, more preferably from about 150 to about 250, even more preferably from about 180 to about 200.
  • polyamide-polyamines useful herein will generally comp ⁇ se from about 0.1% to 8% by the weight of the composition. More preferably, such polyamide-polyamine matenals will compnse from about 0.5% to 4%> by weight of the compositions herein. Most preferably, these polyamide-polyamines will compnse from about 1% to 3% by weight of the composition.
  • polyamide-polyamine matenals used in this invention are those which have repeating, substituted amido-amme units which correspond to the general Structural Formula No I as follows.
  • R [ , R 2 and R5 are each independently C1 - alkylene, C j _4 alkarylene or arylene. It is also possible to eliminate R ⁇ entirely so that the polyamide- polyamme is de ⁇ ved from oxalic acid.
  • R3 is H, epichlorohydnn, an azetidimum group, an epoxypropyl group or a dimethylammohydroxypropyl group
  • R4 can be H, C j ⁇ alkyl, C ⁇ _4 alkaryl, or aryl.
  • R4 may also be any of the foregoing groups condensed with C1.4 alkylene oxide
  • R ⁇ is preferably butylene
  • R 2 and R5 are preferably ethylene.
  • R3 is preferably epichlorohydnn.
  • R4 is preferably H.
  • the polyamide-polyamine matenals useful herein can be prepared by reacting polyamines such as diethylenetnamme, tnethylenetetraamme, tetraethylenepentanune or dipropylenetnamme with C 2 -C 2 dicarboxyhc acids such as oxalic, succmic, glutanc, adipic and diglycolic acids. Such mate ⁇ als may then be further de ⁇ vatized by reaction with, for example, epichlorohydnn. Preparation of such matenals is desc ⁇ bed m greater detail in Keim, U.S. Patent 2,296,116, Issued February 23, 1960; Keim, U.S. Patent 2,296,154, Issued February 23, 1960 and Keim, U.S. Patent 3,332,901, Issued July 25, 1967.
  • polyamide-polyamine agents preferred for use herein are commercially marketed by Hercules, Inc. under the tradename Kymene® . Especially useful are Kymene 557H® and
  • Kymene 557LX® which are epichlorohydnn adducts of polyamide-polyamines which are the reaction products of diethylenetnamme and adipic acid.
  • Other suitable mate ⁇ als are those marketed by Hercules under the tradenames Reten® and Delsette®' and by Sandoz under the tradename Cartaretm®
  • These polyamide-polyamine mate ⁇ als are marketed in the form of aqueous suspensions of the polymenc matenal containing, for example, about 12.5% by weight of solids.
  • Detersive Amme - Suitable amine surfactants for use herein include detersive amines according to the formula: R3 Ri— X— (CH 2 ) n — N
  • R4 wherein Rj is a -C ⁇ 2 alkyl group; n is from about 2 to about 4, X is a bndging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-0(R5)) wherein R5 is H or methyl.
  • Preferred amines include the following:
  • Rj is a Cg-C ⁇ alkyl group and R5 is H or CH3.
  • amme is desc ⁇ bed by the formula:
  • Particularly preferred amines include those selected from the group consisting of octyl amme, hexyl amme, decyl amme, dodecyl amme, Cg-Ci2 b ⁇ s(hydroxyethyl)amme, Cg-Cj2 b ⁇ s(hydroxy ⁇ sopropyl)amme, and Cg-Cj2 amido-propyl dimethyl amine, and mixtures.
  • the detersive amines compnse from about 0.1% to about 10%, preferably from about 0.5%) to about 5%, by weight of the composition.
  • Quaternary Ammonium Surfactants from about 1% to about 6% of a quaternary ammonium surfactant having the formula
  • Rj and R2 are individually selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4 ⁇ ) x H where x has a value from about 2 to about 5; X is an am on; and (1) R3 and R4 are each a Cg-Ci 4 alkyl or (2) R3 is a Cg-C j alkyl, and R4 is selected from the group consisting of C J -C J O alkyl, C J -C J O hydroxy alkyl, benzyl, and -(C2H4 ⁇ ) x H where x has a value from 2 to 5.
  • Prefe ⁇ ed quaternary ammonium surfactants are the chlonde, bromide, and methylsulfate salts.
  • Examples of preferred mono-long chain alkyl quaternary ammonium surfactants are those wherein R ⁇ , R2, and R4 are each methyl and R3 is a Cg-Ci g alkyl; or wherein R3 is Cg.j alkyl and Rj, R 2 , and R4 are selected from methyl and hydroxy-alkyl moieties.
  • ADOGEN 412TM a lauryl tnmethyl ammonium chlo ⁇ de commercially available from Witco, is also preferred. Even more highly preferred are the lauryl t ⁇ methyl ammonium chlonde and mynstyl tnmethyl ammonium chlonde.
  • Alkoxylated quaternary ammonium (AQA) surfactants useful in the present invention are of the general formula:
  • R 1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms
  • R 2 and R 3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl;
  • R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • A is selected from C1 -C4 alkoxy, especially ethoxy (i.e., - CH2CH2O-), propoxy, butoxy and mixtures thereof;
  • p is from 2 to about 30, preferably 2 to about 15, most preferably 2 to about 8; and for formula ⁇ , p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about
  • quaternary surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula:
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH2CH 2 -, -CH 2 CH(CH3)-, -
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, nng structures formed by joining the two
  • R 4 groups -CH 2 CHOHCHOHCOR 6 CHOH-CH 2 OH wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not O; R is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R ⁇ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible amon.
  • Polvefhoxylated-Polvamme Polymers Another polymer dispersant form use herein includes polyethoxyated-polyamme polymers (PPP).
  • the preferred polyethoxylated-polyammes useful herein are generally polyalkyleneammes (PAA's), polyalkyleneimmes (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimmes (PEI's).
  • a common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichlonde, followed by fractional distillation. The common PEA's obtained are t ⁇ ethylenetetramme (TETA) and teraethylenepentamine (TEPA).
  • TETA t ⁇ ethylenetetramme
  • TEPA teraethylenepentamine
  • the cogenencally denved mixture does not appear to separate by distillation and can include other matenals such as cyclic amines and particularly piperazmes. There can also be present cyclic ammes with side chains in which nitrogen atoms appear. See U.S Patent 2,792,372, Dickinson, issued May 14, 1957, which descnbes the preparation of PEA's.
  • Polyethoxylated polyammes can be prepared, for example, by polyme ⁇ zing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfunc acid, hydrogen peroxide, hydrochlonc acid, acetic acid, etc
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfunc acid, hydrogen peroxide, hydrochlonc acid, acetic acid, etc
  • Specific methods for prepanng these polyamme backbones are disclosed m U.S. Patent 2,182,306, Ul ⁇ ch et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951
  • preferred polyethoxyated-polyamme polymers useful for this invention
  • R is selected from linear or branched C 2 -C ⁇ 2 alkylene, C3-C12 hydroxyalkylene, C4-C ⁇ 2 dihydroxyalkylene, Cg-C 12 dialkylarylene, [(CH 2 CH2 ⁇ ) q CH 2 CH2]- and -CH 2 CH(0H)CH 2 0- (CH 2 CH 2 0) q CH 2 CH(OH)CH ]- where q is from about 1 to about 100.
  • Each Rx is independently selected from C1-C4 alkyl, C -C ⁇ alkylaryl, or A.
  • A is of the formula: (CH-CH 2 -0) n B
  • R3 is selected from H or C1 -C3 alkyl, n is from about 5 to about 100, and B is selected from H, C1-C4 alkyl, acetyl, or benzoyl; X is a water soluble amon.
  • R is selected from C4 to Cg alkylene
  • R ⁇ is selected from C ⁇ -
  • R3 where R3 is selected from H or methyl, and n is from about 10 to about 50.
  • R is linear or branched Cg
  • Rj is methyl
  • R3 is H
  • n is from about 20 to about 50.
  • Additional alkoxylated quaternary polyamme dispersants which can be used in the present invention are of the general formula
  • R is selected from linear or branched C 2 -C ⁇ 2 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C 12 dialkylarylene, [(CH 2 CH 2 0) q CH 2 CH 2 ]- and -CH 2 CH(0H)CH 2 0- (CH2CH2 ⁇ ) q CH 2 CH(OH)CH 2 ]- where q is from about 1 to about 100.
  • Each R ⁇ is independently selected from C1 -C4 alkyl, C7-C12 alkylaryl, or A.
  • Rj may be absent on some nitrogens, however, at least three nitrogens must be quatermzed.
  • A is of the formula:
  • R3 where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100 and B is selected from H, C 1-C4 alkyl, acetyl, or benzoyl; m is from about 0 to about 4, and X is a water soluble amon.
  • R is selected from C4 to Cg alkylene
  • Rj is selected from C1 -
  • R3 where R3 is selected from H or methyl, and n is from about 10 to about 50; and m is 1.
  • R is linear or branched Cg
  • R ⁇ is methyl
  • R3 is H
  • n is from about 20 to about 50
  • m is 1.
  • the levels of these polyethoxyated-polyamme polymers used can range from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight.
  • These polyethoxyated- polyamme polymers can be synthesized following the methods outline in U.S. Patent No 4,664,848, or other ways known to those skilled m the art.
  • the anionic surfactant component contains alkyl polyethoxylate sulfates and may contain other non-soap anionic surfactants or mixtures thereof.
  • anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, and m U.S. Patent No. 3,919,678, Laughhn et al, issued December 30, 1975, both incorporated herein by reference.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammomum (e.g., monoethanolammonium or tnethanolammonium) salts, of organic sulfunc reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group.
  • the alkali metal, ammonium and alkylolammomum e.g., monoethanolammonium or tnethanolammonium
  • alkyl is the alkyl portion of aryl groups.
  • alkyl sulfates especially those obtained by sulfatmg the higher alcohols (Cg-C g carbon atoms) such as those produced by reducing the glycendes of tallow or coconut oil.
  • alkyl sulfates especially those obtained by sulfatmg the higher alcohols (Cg-C g carbon atoms) such as those produced by reducing the glycendes of tallow or coconut oil.
  • linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms m the alkyl group is from about 11 to 13, abbreviated as C u - C I3 LAS.
  • anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of a- sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms m the alkane moiety; water-soluble salts of olefin sulfonates containing from about
  • alkyl polyethoxylate sulfates useful herein are of the formula
  • RO(C 2 H 4 0) x S0 3 -M + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 0.5 to about 15.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated C ⁇ 2 -15 pnmary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates. Fatty Acids - Moreover, the anionic surfactant component herein compnses fatty acids.
  • fatty acids include saturated and/or unsaturated fatty acids obtained from natural sources or synthetically prepared.
  • fatty acids include capnc, launc, my ⁇ stic, palmitic, stea ⁇ c, arachidic, and behenic acid.
  • Other fatty acids include palmitoleic, oleic, lmoleic, hnolenic, and ncmoleic acid.
  • Noniomc Detergent Surfactants - Suitable noniomc detergent surfactants are generally disclosed m U.S. Patent 3,929,678, Laughhn et al., issued December 30, 1975, and U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
  • Exemplary, non-limiting classes of useful noniomc surfactants include: Cg-Cjg alkyl ethoxylates ("AE"), with EO about 1-22, including the so-called narrow peaked alkyl ethoxylates and Cg-Cj2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), alkyl dialkyl amine oxide, alkanoyl glucose amide, and mixtures thereof.
  • AE Cg-Cjg alkyl ethoxylates
  • EO alkyl ethoxylates
  • alkyl dialkyl amine oxide alkanoyl glucose amide
  • compositions of the present invention will preferably contain up to about 10%, preferably from 0% to about 5%, more preferably from 0% to about 3%, by weight of an noniomc surfactant.
  • Preferred are the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(0C2H4) n 0H, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms m the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol.
  • noniomc surfactants for use herein include: The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols.
  • the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • noniomc surfactants of this type include Igepal® CO-630, marketed by the GAF Corporation; and Tnton® X-45, X-l 14, X-100, and X-102, all marketed by the Rohm & Haas Company.
  • alkyl phenol alkoxylates These compounds are commonly referred to as alkyl phenol alkoxylates, (e g.. alkyl phenol ethoxylates).
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol.
  • noniomc surfactants of this type include Tergitol® 15-S-9 (the condensation product of Ci 1-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C12-C14 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight distnbution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the condensation product of CJ4-C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The
  • noniomc surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of noniomc surfactant is referred to generally as "alkyl ethoxylates.”
  • alkyl ethoxylates The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • examples of compounds of this type include certain of the commercially-available
  • Pluronic® surfactants marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme consist of the reaction product of ethylenediamme and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000
  • this type of noniomc surfactant include certain of the commercially available Tetromc® compounds, marketed by BASF.
  • Semi-polar noniomc surfactants are a special category of noniomc surfactants which include water-soluble amme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar noniomc detergent surfactants include the amine oxide surfactants having the formula
  • R3(OR 4 ) x N(R5) 2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure.
  • amine oxide surfactants in particular include CjQ- i alkyl dimethyl amine oxides and C -Cj2 alkoxy ethyl dihydroxy ethyl amme oxides.
  • Any reducing saccha ⁇ de containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.)
  • the lntersaccha ⁇ de bonds can be, e.g., between the one position of the additional saccha ⁇ de units and the 2-, 3-, 4-, and or 6- positions on the preceding sacchande units.
  • a polyalkylene-oxide chain joining the hydrophobic moiety and the polysacchande moiety.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysacchandes are octyl, nonyl, decyl, undecyldodecyl, t ⁇ decyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tn-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tn-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
  • the preferred alkylpolyglycosides have the formula
  • R2 ⁇ (C n H 2n O) t (glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably denved from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-pos ⁇ t ⁇ on, preferably predominantly the 2-pos ⁇ t ⁇ on.
  • Fatty acid amide surfactants having the formula: O
  • R 6 -C-N(R 7 ) 2 wherein R" is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C 2 H4 ⁇ ) x H where x vanes from about 1 to about 3.
  • Preferred amides are Cg-C20 ammonia amides, monoethanolamides, dietha-nolamides, and isopropanolamides.
  • Cationic/amphotenc - Non-quaternary, cationic detersive surfactants can also be included in detergent compositions of the present invention.
  • Cationic surfactants useful herein are desc ⁇ bed in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
  • Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly desc ⁇ bed as aliphatic denvatives of secondary or tertiary amines, or aliphatic denvatives of heterocyc c secondary and tertiary ammes in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubihzmg group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
  • Preferred amphotenc include C12 -C j g alkyl ethoxylates
  • AE alkyl ethoxylate
  • Cg-C ⁇ alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
  • C ⁇ -Cjg betames and sulfobetames sultames
  • Ci Q -C j g amme oxides and mixtures thereof.
  • Polyhydroxy Fatty Acid Amide Surfactant -
  • the detergent compositions hereof may also contain polyhydroxy fatty acid amide surfactant.
  • the polyhydroxy fatty acid amide surfactant component comp ⁇ ses compounds of the structural formula:
  • R 2 - C - N - Z wherein: R* IS H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C or C2 alkyl, most preferably Cj alkyl (i.e., methyl), and R 2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be de ⁇ ved from a reducing sugar in a reductive animation reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose,- galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw mate ⁇ als.
  • Z preferably will be selected from the group consisting of -CH2- (CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n . 1 -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)- CH2OH, and alkoxylated denvatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosacchande Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2 -hydroxy ethyl, or N-2 -hydroxy propyl.
  • R -CO-N ⁇ can be, for example, cocamide, steararmde, oleamide, lauramide, my ⁇ stamide, capncamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxygluc ⁇ tyl, 2-deoxyfruct ⁇ tyl, 1-deoxymalt ⁇ tyl, 1-deoxylact ⁇ tyl, 1- deoxygalactityl, 1-deoxymann ⁇ tyl, 1-deoxymaltot ⁇ ot ⁇ tyl, etc.
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive animation reaction to form a corresponding N-alkyl polyhydroxyamme, and then reacting the N-alkyl polyhydroxyamme with a fatty aliphatic ester or tnglyce ⁇ de in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
  • Granular and/or powder laundry detergent compositions preferably comp ⁇ se, in addition to the particulate solids of the present invention, one or more cleaning adjunct mate ⁇ als as described herein.
  • DETERGENT INGREDIENTS CLEANING ADJUNCT MATERIALS
  • the laundry detergent compositions of the present invention as desc ⁇ bed hereinbefore may optionally include, in addition to the particulate solids of the present invention, cleaning adjunct materials desc ⁇ bed below.
  • Biodegradablv branched surfactants The present invention includes important embodiments compnsmg at least one biodegradably branched and/or crystallmity disrupted and/or mid-cham branched surfactant or surfactant mixture.
  • biodegradably branched and/or “crystallmity disrupted” and/or “mid-cham branched” indicate that such surfactants or surfactant mixtures are charactenzed by the presence of surfactant molecules having a moderately non-linear hydrophobe; more particularly, wherein the surfactant hydrophobe is not completely linear, on one hand, nor is it branched to an extent that would result m unacceptable biodegradation.
  • the preferred biodegradably branched surfactants are distinct from the known commercial LAS, ABS, Exxal, Lial, etc. types, whether branched or unbranched.
  • branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe.
  • Typically from one to three such branches can be present on a single hydrophobe, preferably only one.
  • Such biodegradably branched surfactants can have exclusively linear aliphatic hydrophobes, or the hydrophobes can include cycloahphatic or aromatic substitution.
  • MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and linear alkylbenzenesulfonate surfactants said surfactant suitably being selected from m ⁇ d-cham-C C 4 -branched C 8 -C ⁇ 8 -alkyl sulfates, m ⁇ d-cham-C C4-branched C 8 -C ⁇ 8 - alkyl ethoxylated, propoxylated or butoxylated alcohols, m ⁇ d-cha ⁇ n-C ⁇ -C 4 -branched C 8 -C 18 -alkyl ethoxysulfates, m ⁇ d-cha ⁇ n-C ⁇ -C 4 -branched C 8 -C ⁇ 6 -alkyl benzenesulfonates and mixture
  • the biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization.
  • Such surfactants can, general, belong to any known class of surfactants, e.g., anionic, noniomc, cationic, or zwitte ⁇ onic.
  • the biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol.
  • Preferred biodegradably branched surfactants herein m more detail include MCB surfactants as disclosed in the following references: W098/23712 A published 06/04/98 includes disclosure of MCB noniomc surfactants including MCB pnmary alkyl polyoxyalkylenes of formula (1):
  • Such MCB nomonics can alternately include butylene oxide de ⁇ ved moieties, and the -OH moiety can be replaced by any of the well-known end-capping moieties used for conventional noniomc surfactants.
  • R, R 1 3-7C linear alkyl.
  • W097/38957 A also discloses (l) production of MCB alkyl sulphate surfactants by sulphatmg (I) or (II); (n) preparation of MCB alkylethoxy sulphates which compnses ethoxylatmg and then sulphatmg (I) or (II); (in) preparation of MCB alkyl carboxylate surfactants which compnses oxidising (I) or (II) or their aldehyde intermediates and (iv) preparation of MCB acyl taurate, MCB acyl isethionate, MCB acyl sarcosinate or MCB acyl N-methylglucamide surfactants using the branched alkyl carboxylates as feedstock.
  • W097/38956 A published 10/23/97 discloses the preparation of mid- to near mid-cham branched alpha olefins which is effected by: (a) prepanng a mixture of carbon monoxide and hydrogen; (b) reacting this mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a hydrocarbon mixture compnsmg the descnbed olefins; and (c) separating the olefins from the hydrocarbon mixture W097/38956 A further discloses the preparation of mid- to near mid-cham branched alcohols by reacting the olefins descnbed with CO/H 2 under Oxo conditions.
  • These alcohols can be used to prepare (1) MCB sulphate surfactants by sulphatmg the alcohols, (2) MCB alkyl ethoxy sulphates by ethoxylating, then sulphatmg, the alcohols; or (3) branched alkyl carboxylate surfactants by oxidising the alcohols or their aldehyde intermediates.
  • the branched carboxylates formed can be used as a feedstock to prepare branched acyl taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide surfactants, etc.
  • WO97/39091 A published 10/23/97 includes disclosure of a detergent surfactant composition compnsmg at least 0.5 (especially 5, more especially 10, most especially 20) wt% of longer alkyl chain, MCB surfactant of formula (I).
  • WO97/39091 A also discloses a laundry detergent or other cleaning composition compnsmg: (a) 0.001-99% of detergent surfactant (I); and (b) 1 - 99.999% of adjunct ingredients.
  • WO97/39089 A published 10/23/97 includes disclosure of liquid cleaning compositions compnsmg: (a) as part of surfactant system 0.1-50 (especially 1-40) wt % of a mid-chain branched surfactant of formula (I); (b) as the other part of the surfactant system 0 1-50 wt% of co-surfactant(s), (c) 1-99.7 wt% of a solvent; and (d) 0.1-75 wt% of adjunct ingredients.
  • the surfactant composition has an average total number of C atoms in the A-X moiety of 14.5-17.5 (especially 15-17); and B is a hydrophilic moiety selected from sulphates, polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulphates.
  • WO97/39088 A published 10/23/97 includes disclosure of a surfactant composition compnsmg 0.001 - 100%> of MCB pnmary alkyl alkoxylated sulphate(s) of formula (I):
  • WO97/39088 A also discloses (1) a surfactant composition compnsmg a mixture of branched pnmary alkyl sulphates of formula (I) as above.
  • M is a water-soluble cation;
  • Also disclosed is a method for manufactunng longer chain alkyl alkoxylated sulphate surfactant mixture compositions compnsmg alkoxylatmg the specified long chain aliphatic alcohol mixture; sulphatmg the resulting polyoxyalkylene alcohol with S0 3 ; and neutralising the resulting alkyl alkoxylate sulphate acid.
  • the alkyl alkoxylated sulphates may be produced directly from the polyoxyalkylene alcohol by sulphatmg with S0 3 and neutralising.
  • WO 98/23566 A Shell published 06/04/98 discloses branched pnmary alcohol compositions having 8-36 C atoms and an average number of branches per mol of 0.7-3 and compnsmg ethyl and methyl branches.
  • a branched pnmary alkoxylate composition preparable by reacting a branched pnmary alcohol composition as above with an oxirane compound
  • Biodegradably branched surfactants useful herein also include the modified alkylaromatic, especially modified alkylbenzenesulfonate surfactants descnbed in copendmg commonly assigned patent applications (P&G Case Nos. 7303P, 7304P).
  • these surfactants include (P&G Case 6766P) alkylarylsulfonate surfactant systems compnsmg from about 10% to about 100% by weight of said surfactant system of two or more crystalhmty- disrupted alkylarylsulfonate surfactants of formula (B-Ar-D) a (M ( l wherein D is SO3", M is a cation or cation mixture, q is the valence of said cation, a and b are numbers selected such that said composition is electroneutral; Ar is selected from benzene, toluene, and combinations thereof; and B compnses the sum of at least one pnmary hydrocarbyl moiety containing from 5 to 20 carbon atoms and one or more crystallmity-disrupting moieties wherein said crystalhnity- disrupting moieties interrupt or branch from said hydrocarbyl moiety; and wherein said alkylarylsulfonate surfactant system has crystall
  • compositions also include (P&G Case 7303P) surfactant mixtures compnsmg (preferably, consisting essentially of): (a) from about 60% to about 95% by weight (preferably from about 65% to about 90%, more preferably from about 70% to about 85%) of a mixture of branched alkylbenzenesulfonates having formula (I)
  • R 2 is selected from H and C]-C 3 alkyl (preferably H and C C 2 alkyl, more preferably H and methyl, more preferably H and methyl provided that in at least about 0.5, more preferably 0.7, more preferably 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R 2 is H);
  • A is a benzene moiety (typically A is the moiety -C ⁇ H-r , with the S0 3 moiety of Formula (I) m para- position to the L moiety, though in some proportion, usually no more than about 5%, preferably from 0 to 5% by weight, the S0 3 moiety is ortho- to L); and (b) from about 5% to about 60% by weight (preferably from about 10% to about 35%, more preferably from about 15% to about 30%) of a mixture of nonbranched alkylbenzenesulfonates having formula (II
  • surfactant mixtures compnsmg the product of a process compnsmg the steps of: alkylatmg benzene with an alkylatmg mixture; sulfonatmg the product of (I); and neutralizing the product of (II); wherein said alkylatmg mixture compnses: (a) from about 1% to about 99.9%, by weight of branched C 7 -C 20 monoolefins, said branched monoolefins having structures identical with those of the branched monoolefins formed by dehydrogenatmg branched parafins of formula R'LR 2 wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls; R 1 is Ci to C 3 alkyl; and R 2 is selected from H and Ci to C 3 alkyl; and (b) from
  • Bleaching System The laundry compositions of the present invention may compnse a bleaching system.
  • Bleaching systems typically compnse a "bleaching agent” (source of hydrogen peroxide) and an "initiator” or “catalyst".
  • bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition.
  • the amount of bleach activator will typically be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition comprising the bleaching agent-plus-bleach activator
  • Bleaching Agents Hydrogen peroxide sources are descnbed in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp 271-300 "Bleaching Agents (Survey)", and include the vanous forms of sodium perborate and sodium percarbonate, including vanous coated and modified forms.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a preferred percarbonate bleach compnses dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from vanous commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions of the present invention may also compnse as the bleaching agent a chlonne-type bleaching mate ⁇ al.
  • Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC").
  • NaDCC sodium dichloroisocyanurate
  • chlonne-type bleaches are less preferred for compositions which compnse enzymes.
  • Bleach Activators Preferably, the peroxygen bleach component m the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01%, preferably from about 0.5%o, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diam e (TAED), benzoylcaprolactam (BzCL), 4-mtrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C JQ-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
  • TAED tetraacetyl ethylene diam e
  • BzCL benzoylcaprolactam
  • 4-mtrobenzoylcaprolactam 3-
  • Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred hydrophobic bleach activatoYs include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is desc ⁇ bed in U.S. Patent No. 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate
  • Preferred bleach activators are those desc ⁇ bed in U.S. 5,698,504 Ch ⁇ stie et al., issued December 16, 1997; U.S. 5,695,679 Ch ⁇ stie et al. issued December 9, 1997; U.S. 5,686,401
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator the present invention generally ranges from at least 1:1, preferably from about 20: 1, more preferably from about 10: 1 to about 1 : 1, preferably to about 3: 1.
  • Quaternary substituted bleach activators may also be included.
  • the present laundry compositions preferably comp ⁇ se a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA structures are further desc ⁇ bed in U.S. 5,686,015 Willey et al, issued November 1 1, 1997; U.S. 5,654,421
  • bleach activators include: (6- octanam ⁇ docaproyl)oxybenzenesulfonate,(6-nonanam ⁇ docaproyl) oxybenzenesulfonate, (6-decanam ⁇ docaproyl)oxybenzenesulfonate and mixtures thereof.
  • bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5
  • activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffenng agents can be used to secure such pH.
  • Acyl lactam activators as desc ⁇ bed in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al, issued Ap ⁇ l 2, 1996 incorporated herein by reference).
  • compositions and methods may utilize metal-containmg bleach catalysts that are effective for use in bleaching compositions.
  • Preferred are manganese and cobalt-containmg bleach catalysts.
  • One type of metal-contammg bleach catalyst is a catalyst system compnsmg a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zmc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediammetetraacetic acid, ethylenediaminetefra (methylenephosphomc acid) and water-soluble salts thereof
  • ethylenediammetetraacetic acid ethylenediaminetefra (methylenephosphomc acid) and water-soluble salts thereof
  • the compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606, and European Pat. App. Pub. Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al, Preferred examples of these catalysts include
  • metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and U.S. 5,114,611.
  • the use of manganese with various complex hgands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612, 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are desc ⁇ bed, for example, m U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L.
  • cobalt catalyst useful herein are cobalt pentaamme acetate salts having the formula [Co(NH3)5 ⁇ Ac] Ty, wherein "OAc” represents an acetate moiety and “Ty” is an amon, and especially cobalt pentaamme acetate chlo ⁇ de, [Co(NH3)5 ⁇ Ac]Cl2; as well as
  • Transition Metal Complexes of Macropolvcvchc Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycychc ngid hgand.
  • the phrase "macropolycychc ⁇ gid hgand” is sometimes abbreviated as "MRL” in discussion below.
  • the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotes parts per billion by weight and "ppm” denotes parts per million by weight).
  • Suitable transition metals e.g., Mn are illustrated hereinafter.
  • Macropolycychc means a MRL is both a macrocycle and is polycychc
  • Polycychc means at least bicychc.
  • ⁇ gid as used herein herein includes “having a superstructure” and “cross-bndged”. "Rigid” has been defined as the constrained converse of flexibility: see D.H. Busch, Chemical Reviews , (1993), 93, 847-860, incorporated by reference.
  • ⁇ gid as used herein means that the MRL must be determinably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same ring size and type and number of atoms the main nng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's
  • parent macrocycle which is otherwise identical (having the same ring size and type and number of atoms the main nng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's
  • the practitioner will use the free form (not the metal-bound form) of the macrocycles.
  • Rigidity is well-known to be useful in compa ⁇ ng macrocycles; suitable tools for determining, measunng or compa ⁇ ng ⁇ gidity include computational methods (see, for example,
  • Preferred MRL's herein are a special type of ultra-ngid hgand which is cross-bndged.
  • cross-b ⁇ dge is nonhmitmgly illustrated m 1.11 herembelow. In 1.11, the cross-b ⁇ dge is a -
  • Suitable metals m the ⁇ gid hgand complexes include Mn(II), Mn(DI), Mn(IV), Mn(V),
  • transition-metals in the instant transition- metal bleach catalyst include manganese, iron and chromium. More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably compnse:
  • a covalently connected non-metal superstructure capable of increasing the ngidity of the macrocycle, preferably selected from (1) a b ⁇ dgmg superstructure, such as a linking moiety;
  • superstructure is used herein as defined in the literature by Busch et al, see, for example, articles by Busch m "Chemical Reviews”.
  • Preferred superstructures herein not only enhance the ngidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft.
  • Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used.
  • n and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, tnalkylammomum, halogen, mtro, sulfonate, or the like.
  • the aromatic nng m 1.10 can be replaced by a saturated nng, in which the atom m Z connecting into the nng can contain N, O, S or C.
  • Suitable MRL's are further nonhmitmgly illustrated by the following compound:
  • this hgand is named 5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Pamco, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1.
  • Transition-metal bleach catalysts of Macrocychc Rigid Ligands which are suitable for use in the invention compositions can m general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and non-hmitmgly illustrated by any of the following: D ⁇ chloro-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane Manganese(D) D ⁇ aquo-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6 6.2]hexadecaneManganese(D)
  • Hexafluorophosphate D ⁇ chloro-5,12-d ⁇ -n-butyl-l,5,8,12-tetraaza b ⁇ cyclo[6.6.2]hexadecaneManganese(II) D ⁇ chloro-5,12-d ⁇ benzyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecaneManganese(II) D ⁇ chloro-5-n-butyl-12-methyl-l,5,8,12-tetraaza-b ⁇ cyclo[6.6.2]hexadecane
  • Manganese(D) D ⁇ chloro-5-n-octyl-12-methyl-l,5,8,12-tetraaza-b ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) D ⁇ chloro-5-n-butyl-12-methyl-l,5,8,12-tetraaza-b ⁇ cyclo[6.6.2]hexadecane
  • Manganese(D) D ⁇ chloro-5-n-octyl-12-methyl-l,5,8,12-tetraaza-b ⁇ cyclo[6.6.2]hexadecane
  • compositions and laundry processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will comp ⁇ se from about 0.0005%> to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions.
  • compositions herein may comp ⁇ se one or more other bleach catalysts.
  • Preferred bleach catalysts are zwittenonic bleach catalysts, which are descnbed in U.S. Patent No. 5,576,282 (especially 3-(3,4-d ⁇ hydro ⁇ soqumohn ⁇ um) propane sulfonate.
  • Other bleach catalysts include cationic bleach catalysts are desc ⁇ bed in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.
  • Bleach Boosting Compounds may compnse one or more bleach boosting compounds.
  • Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications.
  • the bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness.
  • Suitable bleach boosting compounds for use in accordance with the present invention comprise cationic lmines, zwittenonic -mines, anionic lmines and/or polyionic mimes having a net charge of from about +3 to about -3, and mixtures thereof.
  • imme bleach boosting compounds of the present invention include those of the general structure:
  • R ⁇ - R 4 may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocychc nng, alkyl and cycloalkyl radicals.
  • Preferred bleach boosting compounds include where Rl - R 4 may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocychc nng, alkyl and cycloalkyl radicals except that at least one of R* - R 4 contains an amonically charged moiety.
  • More preferred bleach boosting compounds include the amonically charged moiety bonded to the imme nitrogen.
  • Such bleach boosting compounds comp ⁇ se quaternary imme zwitte ⁇ ons represented by the formula:
  • Rl - R ⁇ is hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocychc nng, alkyl and cycloalkyl radicals; R ⁇ and R2 form part of a common nng; T has the formula. wherein x is equal to 0 or 1 ; J, when present, is selected from the group consisting of
  • R 7 -R*6 are individually selected from the group consisting of H, linear or branched Ci -C j g substituted or unsubstituted alkyl, alkylene, oxyalkylene, aryl, substituted aryl, substituted arylcarbonyl groups and amide groups; Z is covalently bonded to J x when x is 1 and to Cj, when x is 0, and Z is selected from the group consisting of -CO2", -S ⁇ 3"and -OS03 " and a is 1. R ⁇ and R2 together may form the non- charged moiety:
  • Most preferred bleach boosting compounds include are ary mmium zwittenons wherein R3 is H, Z is -SO3" or -OSO3", and a is 1.
  • the aryhmmium zwittenons may have the fo ⁇ nula:
  • R* 7 is selected from the group consisting of H and linear or branched Ci -Cjg substituted or unsubstituted alkyl, preferably C J-C14 alkyl and even more preferably Cg-Ci Q linear alkyl chain.
  • the bleach boosting compounds may also compnse an aryhmmum polyion having a net negative charge and R 3 is H, T is -(CH2)t>- or -CH2(C6H4)-, Z is -SO3- , a is 2 and b is from 2 to 4
  • the aryhmmium polyion preferably has the formula:
  • the quaternary imme bleach boosting compounds preferably act m conjunction with a peroxygen source to provide a more effective bleaching system.
  • the bleach boosting compounds react with the peroxygen source to form a more active bleaching species, an oxazindimum compound.
  • the formed oxazindimum compounds are either cationic, zwittenonic or polyionic with a net negative charge as was the imme bleach boosting compound.
  • the oxazindimum compound has an increased activity at lower temperatures relative to the peroxygen compound.
  • the oxazindimum compound is represented by the formula:
  • the preferred bleach boosting compounds of the present invention represented by the formula (D) produces the active oxazindimum bleaching species represented by the formula (IV)
  • R ⁇ 7 is defined as above.
  • Peroxygen sources are well-known m the art and the peroxygen source employed m the present invention may comp ⁇ se any of these well known sources, including peroxygen compounds as well as compounds which under consumer use conditions provide an effective amount of peroxygen m situ.
  • the peroxygen source may include a hydrogen peroxide source, the in situ formation of a peracid amon through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources.
  • a hydrogen peroxide source the in situ formation of a peracid amon through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources.
  • the bleach boosting compounds when present, are preferably employed m conjunction with a peroxygen source in the bleaching compositions of the present invention.
  • the peroxygen source is preferably present at a level of from about 0.1% to about 60% by weight of the composition, and more preferably from about 1% to about 40%> by weight of the composition.
  • the bleach boosting compound is preferably present at a level of from about 0.01% to about 10% by weight of the composition, and more preferably from about 0.05% to about 5% by weight of the composition.
  • PAP phthalimido-peroxy-caproic acid
  • the preferred enzymes for use in the particulate solids of the present invention are selected from proteases, amylases, cellulases and mixtures thereof
  • Non miting examples of other suitable enzymes include the following:
  • Suitable enzymes include ? but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, hpases, phosphohpases, esterases, cutmases, pectmases, keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgnmases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases, hyaluromdase, chondroitmase, laccase, mannanases, more preferably plant cell wall degrading enzymes and non- cell wall-degrading enzymes (WO 98/39403 A) and can, more specifically, include pectmase (WO 98/06808 A, JP10088472 A, JP10088485 A); pectolyase (WO98/068
  • Oxidoreductases and/or their associated antibodies can be used, for example with H 2 0 2 , as taught in WO 98/07816 A.
  • other redox-active enzymes can be used, even, for example, catalases (see, for example JP09316490 A).
  • any oxygenases of extracellular ongm especially fungal oxygenase such as dioxygenase of extracellular ongm.
  • the latter is most especially quercetinase, catechmase or an anthocyanase, optionally in combination with other suitable oxidase, peroxidase or hydrolytic enzymes, all a taught in WO9828400 A2.
  • cellulases useful in the present invention include both bactenal or fungal cellulases.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola msolens, T ⁇ choderma, Thielavia and Sporotnchum.
  • EP 739 982 descnbes cellulases isolated from novel Bacillus species.
  • Suitable cellulases are also disclosed m GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola g ⁇ sea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Suitable cellulases are cellulases o ⁇ gmated from Humicola msolens having a molecular weight of about 50KDa, an isoelectnc point of 5.5 and containing 415 ammo acids; and a "43kD endoglucanase denved from Humicola msolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the ammo acid sequence disclosed in WO 91/17243
  • suitable cellulases are the EGIQ cellulases from Tnchoderma longibrachiatum descnbed in WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits.
  • cellulases examples include cellulases desc ⁇ bed in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also W091/17244 and WO91/21801. Other suitable cellulases for fabnc care and/or laundry properties are descnbed in WO96/34092, W096/17994 and W095/24471.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-containmg detergent compositions are disclosed, for example, in U.S.
  • Suitable enhancers are selected from the group consisting of substituted phenthiazine and phenoxasme 10-Phenoth ⁇ az ⁇ neprop ⁇ on ⁇ cac ⁇ d (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazmepropionic acid (POP) and 10-methylphenoxazme (descnbed m WO
  • Enzymatic systems may be used as bleaching agents.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or dunng the washing and/or nnsmg process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed m EP Patent Application 91202655.6 filed
  • Suitable hpase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzen ATCC 19.154, as disclosed in Bntish Patent 1,372,034.
  • Suitable hpases include those which show a positive immunological cross-reaction with the antibody of the hpase, produced by the microorganism Pseudomonas fluorescent LAM 1057. This hpase is available from Amano Pharmaceutical Co. Ltd, Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano- P".
  • hpases include Amano-CES, hpases ex Chromobacter viscosum, e.g. Chromobacter viscosum var polyticum NRRLB 3673 from Toyo Jozo Co, Tagata, Japan, Chromobacter viscosum hpases from U.S. Biochemical Corp, U.S.A. and Disoynth Co, The Netherlands, and hpases ex Pseudomonas gladioli.
  • hpases are hpases such as
  • Ml Lipase* - which have found to be very effective when used m combination with the compositions of the present invention. Also suitable are the hpolytic enzymes desc ⁇ bed in EP 258 068, WO 92/05249 and
  • cutmases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely hpases which do not require mterfacial activation. Addition of cutmases to laundry compositions have been desc ⁇ bed in e.g. WO-A-88/09367 (Genencor); WO 90/09446
  • phosphohpases may be incorporated into the laundry compositions of the present invention.
  • suitable phosphohpases included: EC 3.1.1 32 Phosphohpase Al; EC 3.1.1 4 Phosphohpase A2; EC 3.1 1.5 Lysophohpase; EC 3.1.4 3 Phosphohpase C; EC 3.1.4.4.
  • Phospohpase D Commercially available phosphohpases include LECITASE® from Novo Nordisk A/S of Denmark and Phosphohpase A2 from Sigma. When phospohpases are included in the compositions of the present invention, it is preferred that amylases are also included.
  • the combined action of the phosphohpase and amylase provide substantive stain removal, especially on greasy/oily, starchy and highly colored stams and soils.
  • the phosphohpase and amylase when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500: 1 and 1:5, more preferably between 50: 1 and 1 : 1.
  • Suitable proteases are the subtihsms which are obtained from particular strains of B subtihs and B. licheniformis (subti sin BPN and BPN')
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo".
  • the preparation of this enzyme and analogous enzymes is descnbed in GB 1,243,784 to Novo.
  • Proteolytic enzymes also encompass modified bactenal se ⁇ ne proteases, such as those descnbed in European Patent Application Senal Number 87 303761.8, filed Ap ⁇ l 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and m European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bactenal senne proteolytic enzyme which is called "Protease A" herein.
  • Protease C is a va ⁇ ant of an alkaline senne protease from Bacillus in which Lysine replaced argmine at position 27, tyrosme replaced valme at position 104, senne replaced asparagme at position 123, and alanine replaced threomne at position 274.
  • Protease C is desc ⁇ bed in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified vanants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase as descnbed m U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase vanant of the protease descnbed in WO95/10591, having an ammo acid sequence denved by replacement of a plurality of ammo acid residues replaced in the precursor enzyme corresponding to position +210 m combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occur ⁇ ng subtihsm from Bacillus amylohquefaciens or to equivalent ammo acid residues in
  • proteases desc ⁇ bed in patent applications EP 251 446 and WO 91/06637, protease BLAP® desc ⁇ bed in WO91/02792 and their va ⁇ ants described in WO 95/23221
  • protease from Bacillus sp. NCIMB 40338 desc ⁇ bed m WO 93/18140 A to Novo.
  • Enzymatic detergents compnsmg protease, one or more other enzymes, and a reversible protease inhibitor are desc ⁇ bed in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as desc ⁇ bed in WO 95/07791 to Procter & Gamble.
  • a recombmant trypsm-hke protease for detergents suitable herein is desc ⁇ bed in WO 94/25583 to Novo.
  • Other suitable proteases are descnbed in EP 516 200 by Unilever.
  • proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo
  • MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
  • Preferred proteases useful herein include certain vanants ( WO 96/28566 A; WO 96/28557 A, WO 96/28556 A; WO 96/25489 A).
  • Other particularly useful proteases are multiply-substituted protease vanants compnsmg a substitution of an ammo acid residue with another naturally occur ⁇ ng ammo acid residue at an ammo acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtihsin in combination with a substitution of an ammo acid residue with another naturally occurnng ammo acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104,
  • protease va ⁇ ant includes a substitution set selected from the group consisting of:
  • protease vanant includes a substitution set selected from the group consisting of:
  • protease va ⁇ ant includes the substitution set 101/103/104/159/232/236/245/248/252, preferably 101G/103A 104I/159D/232V/ 236H/245R 248D/252K
  • protease from Bacillus sp. NCIMB 40338 desc ⁇ bed in WO 93/18140 A to Novo.
  • Enzymatic detergents compnsmg protease, one or more other enzymes, and a reversible protease inhibitor are descnbed WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as desc ⁇ bed m WO 95/07791 to Procter & Gamble.
  • a recombmant trypsin-hke protease for detergents suitable herein is desc ⁇ bed in WO 94/25583 to Novo.
  • Other suitable proteases are descnbed in EP 516 200 by Unilever.
  • proteases useful m the present invention are known as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands). Bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP 756,000 A) are also useful.
  • enzymes and their directly linked inhibitors e.g., protease and its inhibitor linked by a peptide chain as desc ⁇ bed m WO 98/13483 A
  • enzymes and their non-lmked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide denvatives as descnbed in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
  • Amylases can be used with amylase antibodies as taught m WO 98/07818 A and WO 98/07822 A, hpases can be used in conjunction with lipase antibodies as taught in WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, Cellulase can be combined with cellulase antibodies as taught in WO 98/07823 A and WO 98/07821 A. More generally, enzymes can be combined with similar or dissimilar enzyme directed antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A.
  • the prefe ⁇ ed enzymes herein can be of any suitable ongm, such as vegetable, animal, bactenal, fungal and yeast ongin.
  • Preferred selections are influenced by factors such as pH-activity and or stability optima, thermostabi ty, and stability to active detergents, builders and the like.
  • bactenal or fungal enzymes are preferred, such as bactenal amylases and proteases, and fungal cellulases
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO94/02597 desc ⁇ bes laundry compositions which incorporate mutant amylases. See also W095/ 10603.
  • Other amylases known for use m laundry compositions include both ⁇ - and ⁇ - amylases.
  • ⁇ -Amylases are known in the art and include those disclosed m US Pat. no. 5,003,257, EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and B ⁇ tish Patent specification no. 1,296,839 (Novo).
  • amylases are stability-enhanced amylases descnbed in W094/18314 and WO96/05295, Genencor, and amylase vanants having additional modification m the immediate parent available from Novo Nordisk A S, disclosed in WO 95/10603. Also suitable are amylases descnbed in EP 277 216. Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and
  • Termamyl®, Ban® ,Fungamyl® and Duramyl® all available from Novo Nordisk A S Denmark.
  • W095/26397 descnbes other suitable amylases : ⁇ -amylases charactensed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°
  • thermostabihty and a higher activity level are desc ⁇ bed m W095/35382.
  • compositions of the present invention may also comp ⁇ se a mannanase enzyme.
  • the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1.78 : Endo-l,4- ⁇ -mannos ⁇ dase, referred therein after as "mannanase” and EC 3.2.1.100 : 1 ,4- ⁇ -mannob ⁇ os ⁇ dase and mixtures thereof. (IUPAC
  • the treating compositions of the present invention when a mannanase is present, comp ⁇ se a ⁇ -l,4-Mannos ⁇ dase (E.C. 3.2.1.78) referred to as Mannanase.
  • Mannanase or "galactomannanase” denotes a mannanase enzyme defined according to the art as officially being named mannan endo-l,4-beta-mannos ⁇ dase and having the alternative names beta-mannanase and endo-l,4-mannanase and catalysing the reaction: random hydrolysis of 1,4- beta-D- mannosidic linkages m mannans, galactomannans, glucomannans, and galactoglucomannans.
  • Mannanases (EC 3.2 1.78) Constitute a group of polysaccharases which degrade mannans and denote enzymes which are capable of cleaving polyose chains contanmg mannose units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-mannans.
  • Mannans are polysaccha ⁇ des having a backbone composed of ⁇ -1,4- linked mannose; glucomannans are polysacchandes having a backbone or more or less regularly alternating ⁇ -1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with ⁇ -1,6 linked galactose sidebranches. These compounds may be acetylated.
  • the degradation of galactomannans and galactoglucomannans is facilitated by full or partial removal of the galactose sidebranches. Further the degradation of the acetylated mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases.
  • the oligomers which are released from the mannanases or by a combination of mannanases and ⁇ - galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by ⁇ -mannosidase and/or ⁇ -glucosidase.
  • Mannanases have been identified in several Bacillus organisms. For example, Talbot et al, Appl. Environ. Microbiol, Vol.56, No. 11, pp. 3505-3510 (1990) descnbes a beta-mannanase denved from Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al. World J. Microbiol. Biotech, Vol. 10, No. 5, pp.
  • JP-03047076 discloses a beta- mannanase denved from Bacillus sp, having a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pi of 5.3-5.4.
  • JP-63056289 descnbes the production of an alkaline, thermostable beta-mannanase which hydrolyses beta-l,4-D-mannopyranos ⁇ de bonds of e.g.
  • JP-63036774 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at an alkaline pH.
  • JP-08051975 discloses alkaline beta-mannanases from alkalophihc Bacillus sp. AM- 001.
  • a pu ⁇ fied mannanase from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is disclosed in WO 97/11164.
  • WO 91/18974 descnbes a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature.
  • WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or modification of plant or algae cell wall matenal.
  • WO 93/24622 discloses a mannanase isolated from Tnchoderma reseei useful for bleaching hgnocellulosic pulps.
  • mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase ong atmg from a bactenal source.
  • the laundry detergent composition of the present invention will compnse an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12.
  • Most preferred mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme ongmatmg from Bacillus sp. 1633 as desc ⁇ bed in the co-pendmg Danish patent application No. PA 1998 01340.
  • alkaline mannanase enzyme is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
  • the alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is desc ⁇ bed in the co-pendmg U.S. patent application se ⁇ al No. 09/111,256. More specifically, this mannanase is: l) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or n) a polypeptide compnsmg an amino acid sequence as shown m positions 32-343 of SEQ ID NO:2 as shown in U.S. patent application senal No.
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO 2 from ammo acid residue 32 to amino acid residue 343 as shown m U S. patent application senal No 09/111,256,
  • a second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is desc ⁇ bed in the co-pending U.S. patent application senal No. 09/095,163. More specifically, this mannanase is: l) is encoded by the coding part of the DNA sequence shown in SED ID No. 5 shown in the U.S. patent application senal No. 09/095,163 or an analogue of said sequence; and/or n) a polypeptide compnsmg an ammo acid sequence as shown SEQ ID NO:6 shown in the U.S. patent application senal No.
  • 09/095,163 or in) an analogue of the polypeptide defined in u) which is at least 70% homologous with said polypeptide, or is denved from said polypeptide by substitution, deletion or addition of one or several ammo acids, or is lmmunologically reactive with a polyclonal antibody raised against said polypeptide m pu ⁇ fied form.
  • the corresponding isolated polypeptide having mannanase activity selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and compnsmg a sequence of nucleotides as shown in SEQ ID NO:5 as shown in the U.S. patent application senal No 09/095,163
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the ammo acid sequence of SEQ ID NO
  • mannanase degenerate nucleotide sequences of (a), (b), (c) or (d)
  • a third more preferred mannanase is desc ⁇ bed m the co-pending Danish patent application No PA 1998 01340. More specifically, this mannanase is: 0 a polypeptide produced by Bacillus sp 1633; n) a polypeptide compnsmg an ammo acid sequence as shown in positions 33-340 of SEQ ID NO:2 as shown in the Danish application No.
  • PA 1998 01340 or in) an analogue of the polypeptide defined in l) or n) which is at least 65% homologous with said polypeptide, is denved from said polypeptide by substitution, deletion or addition of one or several amino acids, or is lmmunologically reactive with a polyclonal antibody raised against said polypeptide m pu ⁇ fied form.
  • analogue of the polypeptide defined in l) or n) which is at least 65% homologous with said polypeptide is denved from said polypeptide by substitution, deletion or addition of one or several amino acids, or is lmmunologically reactive with a polyclonal antibody raised against said polypeptide m pu ⁇ fied form.
  • the corresponding isolated polynucleotide molecule selected from the group consisting of:
  • the plasmid pBXM3 compnsmg the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition number DSM 12197.
  • a fourth more preferred mannanase is desc ⁇ bed in the Danish co-pendmg patent application No. PA 1998 01341. More specifically, this mannanase is: I) a polypeptide produced by Bacillus sp. AAI 12; n) a polypeptide compnsmg an amino acid sequence as shown in positions
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the ammo acid sequence of SEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 as shown m the Danish application No. PA 1998 01341; (d) molecules complementary to (a), (b) or (c); and
  • the plasmid pBXMl compnsmg the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorgamsmen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the deposition number DSM 12433.
  • the mannanase when present, is incorporated into the treating compositions of the present invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition.
  • compositions of the present invention may also comp ⁇ se a xyloglucanase enzyme
  • Suitable xyloglucanases for the purpose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition.
  • the term "endoglucanase activity” means the capability of the enzyme to hydrolyze 1,4- ⁇ -D-glycos ⁇ d ⁇ c linkages present in any cellulosic mate ⁇ al, such as cellulose, cellulose denvatives, lichemn, ⁇ -D-glucan, or xyloglucan.
  • the endoglucanase activity may be determined m accordance with methods known in the art, examples of which are descnbed in WO 94/14953 and hereinafter.
  • One unit of endoglucanase activity e.g. CMCU, AVIU, XGU or BGU
  • CMCU CMC
  • AVIU acid swollen Avicell
  • XGU xyloglucan
  • BGU cereal ⁇ -glucan
  • the reducing sugars are determined as desc ⁇ bed in WO 94/14953 and hereinafter.
  • the specific activity of an endoglucanase towards a substrate is defined as units/mg of protein.
  • I) is encoded by a DNA sequence compnsmg or included in at least one of the following partial sequences
  • the term "specific for xyloglucan” means that the endoglucanse enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less than 75% activity, more preferably less than 50%> activity, most preferably less than about 25% > activity, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans.
  • the specificity of an endoglucanase towards xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimal conditions obtained by incubation of the enzyme with xyloglucan and the other substrate to be tested, respectively.
  • the specificity may be defined as the xyloglucan to ⁇ -glucan activity (XGU/BGU), xyloglucan to carboxy methyl cellulose activity (XGU/CMCU), or xyloglucan to acid swollen Avicell activity (XGU/ AVIU), which is preferably greater than about 50, such as 75, 90 or 100.
  • strain CBS 101 43 an endoglucanase produced by strain CBS 101 43, but also an endoglucanase encoded by a DNA sequence isolated from strain CBS 101 43 and produced in a host organism transformed with said DNA sequence.
  • homologue indicates a polypeptide encoded by DNA which hyb ⁇ dizes to the same probe as the DNA coding for an endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as presoakmg in 5xSSC and prehybndizmg for 1 h at -40°C in a solution of 5xSSC, 5xDenhardt's solution, and 50 ⁇ g of denatured sonicated calf thymus DNA, followed by hyb ⁇ dization in the same solution supplemented with 50 ⁇ Ci 32-P-dCTP labelled probe for 18 h at -40°C and washing three times in 2xSSC, 0.2% SDS at 40°C for 30 minutes).
  • the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%>, at least 80%, at least 85%, at least 90%> or even at least 95% with any of the sequences shown above.
  • the term is intended to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions which do not give nse to another ammo acid sequence of the polypeptide encoded by the sequence, but which correspond to the codon usage of the host organism into which a DNA construct compnsmg any of the DNA sequences is introduced or nucleotide substitutions which do give nse to a different ammo acid sequence and therefore, possibly, a different ammo acid sequence and therefore, possibly, a different protein structure which might give nse to an endoglucanase mutant with different properties than the native enzyme.
  • Endoglucanase specific for xyloglucan useful in the present invention preferably is one which has a XGU/BGU, XGU/CMU and or XGU/ AVIU ratio (as defined above) of more than 50, such as 75, 90 or 100.
  • endoglucanase specific for xyloglucan is preferably substantially devoid of activity towards ⁇ -glucan and/or exhibits at the most 25% such as at the most 10%> or about 5%, activity towards carboxymethyl cellulose and or Avicell when the activity towards xyloglucan is 100%.
  • endoglucanase specific for xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity which has been observed for most endoglucanases specific for xyloglucan of plant ongin Endoglucanase specific for xyloglucan may be obtained from the fungal species A.
  • Microbial endoglucanases specific for xyloglucan has also been descnbed in WO 94/14953.
  • Endoglucanases specific for xyloglucan from plants have been desc ⁇ bed, but these enzymes have transferase activity and therefore must be considered infe ⁇ or to microbial endoglucanses specific for xyloglucan whenever extensive degradation of xyloglucan is desirable.
  • An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts in a microbial host, than enzymes of other ongins.
  • the xyloglucanase when present, is incorporated into the treating compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable ongm, such as vegetable, animal, bactenal, fungal and yeast ongm.
  • Ongm can further be mesophihc or extremophihc (psychrophihc, psychrotrophic, thermophihc, barophihc, alkalophi c, acidophi c, halophihc, etc.). Punfied or non-pu ⁇ fied forms of these enzymes may be used.
  • the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the vanant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme vanant is tailored to suit the particular laundry application.
  • the isoelect ⁇ c point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase m isoelect ⁇ c point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt bndges and enforcing calcium binding sites to increase chelant stability.
  • Suitable cleaning adjunct matenals that can be added are enzyme oxidation scavengers.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme matenals are also disclosed in WO 9307263 and WO 9307260 to
  • Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also descnbed, for example, m U.S. 3,519,570.
  • ⁇ A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is desc ⁇ bed m WO 9401532
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115 and 5,576,282.
  • compositions descnbed herein preferably comp ⁇ se one or more detergent builders or builder systems.
  • the compositions will typically comp ⁇ se at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to about 30% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Preferred builders for use m the detergent and laundry compositions, particularly dishwashing compositions, descnbed herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as descnbed in U.S. Patent Nos. 5,695,679, 5,705,464 and 5,710,115.
  • water-soluble builder compounds for example polycarboxylates
  • polycarboxylates for example polycarboxylates
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.
  • Inorganic or P-contaming detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tnpolyphosphates, pyrophosphates, and glassy polymenc meta-phosphates), phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surp ⁇ smgly well even m the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • Suitable silicates include the water-soluble sodium silicates with an S ⁇ 0 2 :Na 2 0 ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 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 S ⁇ 0 2 :Na 0 ratio of 2.0 is the most preferred.
  • Silicates, when present, are preferably present in the detergent and laundry compositions desc ⁇ bed herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.
  • Partially soluble or insoluble builder compounds which are suitable for use in the detergent and laundry compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates (partially water-soluble) as desc ⁇ bed m U.S. Patent No. 4,664,839, and sodium alummosilicates (water-insoluble).
  • these builders are typically present at a level of from about 1% to 80% by weight, preferably from about 10% to 70% by weight, most preferably from about 20% to 60% by weight of the composition.
  • Crystalline layered sodium silicates having the general formula NaMS ⁇ x ⁇ 2 x + ⁇ -yH2 ⁇ wherein M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used in the compositions desc ⁇ bed herein.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed m DE-A- 3417649 and DE-A-3742043.
  • the most preferred mate ⁇ al is delta-Na2S ⁇ 5, available from
  • NaSKS-6 Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2S ⁇ 5 morphology form of layered silicate. SKS-6 is a highly preferred layered silicate for use m the compositions descnbed herein herein, but other such layered silicates, such as those having the general formula NaMS ⁇ x ⁇ 2 x + ⁇ -yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used m the compositions desc ⁇ bed herein.
  • Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2S ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a cnspenmg agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • the crystalline layered sodium silicate mate ⁇ al is preferably present in granular detergent compositions as a particulate m intimate admixture with a solid, water-soluble lomzable mate ⁇ al.
  • the solid, water-soluble lomzable mate ⁇ al is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • Alummosihcate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Alummosihcate builders have the empincal formula- [M z (A10 2 ) y ]-xH 2 0 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.
  • the alummosihcate builder is an alummosihcate zeolite having the unit cell formula: Na z [(A10 2 ) z (S ⁇ 0 2 ) y ] xH 2 0 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 7.5 to 276, more preferably from 10 to 264.
  • the alummosihcate builders are preferably in hydrated form and are preferably crystalline, containing from about 10% to about 28%o, more preferably from about 18% to about 22% water in bound form.
  • alummosihcate ion exchange mate ⁇ als can be crystalline or amorphous in structure and can be naturally-occumng alummosilicates or synthetically denved.
  • a method for producing alummosihcate ion exchange matenals is disclosed in U.S. 3,985,669.
  • Preferred synthetic crystalline alummosihcate ion exchange mate ⁇ als useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP and Zeolite HS and mixtures thereof.
  • the crystalline alummosihcate ion exchange matenal has the formula:
  • x is from about 20 to about 30, especially about 27.
  • This matenal is known as Zeolite A.
  • the alummosihcate has a particle size of about 0.1-10 microns m diameter.
  • Zeolite X has the formula:
  • Citrate builders e.g., cit ⁇ c acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccmates are also especially useful in such compositions and combinations
  • succmic acid builders include the C5-C20 alkyl and alkenyl succmic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succmate builders include- laurylsuccmate, mynstylsuccinate, palmitylsuccmate, 2- dodecenylsuccmate (preferred), 2-pentadecenylsuccmate, and the like. Laurylsuccmates are the preferred builders of this group, and are desc ⁇ bed in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C ⁇ -Cjg monocarboxyhc acids
  • the aforesaid builders especially citrate and/or the succmate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsmg, which should be taken into account by the formulator.
  • Dispersants - One or more suitable polyalkyleneimine dispersants may be incorporated into the laundry compositions of the present invention.
  • suitable dispersants can be found in European Patent Application Nos. 111,965, 111,984, and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145.
  • any suitable clay/soil dispersent or anti- redepostion agent can be used in the laundry compositions of the present invention.
  • polymenc dispersing agents which include polymenc polycarboxylates and polyethylene glycols, are suitable for use m the present invention.
  • Unsaturated monome ⁇ c acids that can be polymenzed to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhydnde), fumanc acid, itaconic acid, acomtic acid, mesaconic acid, citracomc acid and methylenemalomc acid.
  • Particularly suitable polymenc polycarboxylates can be denved from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water- soluble salts of polymenzed acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known mate ⁇ als. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, m U.S. 3,308,067.
  • Acryhc/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such mate ⁇ als include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30: 1 to about 1 : 1, more preferably from about 10: 1 to 2.1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known matenals which are descnbed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers compnsmg hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol terpolymers.
  • Such mate ⁇ als are also disclosed m EP 193,360, including, for example, the 45/45/10 terpolymer of acryhc/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about
  • 100,000 preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially m conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions according to the present invention may optionally comp ⁇ se one or more soil release agents. If utilized, soil release agents will generally comp ⁇ se from about 0.01%, preferably from about 0.1 %>, more preferably from about 0.2%> to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition.
  • soil release agents will generally comp ⁇ se from about 0.01%, preferably from about 0.1 %>, more preferably from about 0.2%> to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition.
  • suitable soil release polymers are disclosed m: U.S. Patent Nos.
  • compositions of the present invention herein may also optionally contain a chelatmg agent which serves to chelate metal ions and metal expedities which would otherwise tend to deactivate the bleaching agent(s).
  • a chelatmg agent which serves to chelate metal ions and metal interruptionties which would otherwise tend to deactivate the bleaching agent(s).
  • Useful chelatmg agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelatmg agents and mixtures thereof. Further examples of suitable chelatmg agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.
  • compositions herein may also contain water-soluble methyl glycme diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
  • MGDA water-soluble methyl glycme diacetic acid
  • these chelatmg agents will generally compnse from about 0.1%. to about 15%, more preferably from about 0 1% to about 3.0% by weight of the detergent compositions herein Suds suppressor - Another optional ingredient is a suds suppressor, exemplified by sihcones, and sihca-sihcone mixtures Examples of suitable suds suppressors are disclosed in
  • Softening agents - Fabnc softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention.
  • Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and m U.S. 5,019,292
  • Organic softening agents include the water insoluble tertiary am es as disclosed m GB-A-1 514 276 and EP-B-011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-026 527 and EP-B-026 528 and di-long-chain amides as disclosed m EP-B-0 242 919.
  • Other useful organic ingredients of fabnc softening systems include high molecular weight polyethylene oxide mate ⁇ als as disclosed m EP-A-0 299 575 and 0 313 146.
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the mate ⁇ al being added as a dry mixed component to the remainder of the formulation.
  • Organic fabnc softening agents such as the water-insoluble tertiary ammes or dilong chain amide mate ⁇ als are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide mate ⁇ als and the water soluble cationic matenals are added at levels of from 0.1% to 2%>, normally from 0.15% to 1.5% by weight.
  • A-239 910 have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlondes and methyl sulfates.
  • Non-hmitmg examples of softener-compatible anions for the quaternary ammonium compounds and amme precursors include chlo ⁇ de or methyl sulfate.
  • Dye transfer inhibition The detergent compositions of the present invention can also include compounds for inhibiting dye transfer from one fabnc to another of solubihzed and suspended dyes encountered dunng fabnc laundenng and conditioning operations involving colored fabncs.
  • i Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention can also comp ⁇ se from 0 001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymenc dye transfer inhibiting agents.
  • Said polymenc dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fab ⁇ cs onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fab ⁇ cs before the dyes have the opportunity to become attached to other articles in the wash.
  • Especially suitable polymenc dye transfer inhibiting agents are polyamme N-oxide polymers, copolymers of N-vmylpyrrohdone and N-vmyhmidazole, polyvmylpyrrohdone polymers, polyvmyloxazohdones and polyvmylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are disclosed in U.S. Patent Nos. 5,707,950 and 5,707,951.
  • Additional suitable dye transfer inhibiting agents include, but are not limited to, cross- linked polymers.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been descnbed in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made in such a way that they form a three-dimensional ngid structure, which can entrap dyes in the pores formed by the three- dimensional structure.
  • the cross-linked polymers entrap the dyes by swelling.
  • Such cross-linked polymers are desc ⁇ bed in the co-pending European patent application 94870213.9.
  • Mate ⁇ als - Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more matenals for assisting or enhancing laundry performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions.
  • Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals compnse, in total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as non-phosphate builders, color speckles, silvercare, anti-tarmsh and or anti-corrosion agents-, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, solubihzmg agents, earners, processing aids, pigments, and pH control agents as described m U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and
  • the invention herein also encompasses a laundenng pretreatment process for fabncs which have been soiled or stained compnsmg directly contacting said stams and/or soils with a highly concentrated form of the laundry composition set forth above pnor to washing such fab ⁇ cs using conventional aqueous washing solutions.
  • the laundry composition remains in contact with the soil/stam for a pe ⁇ od of from about 30 seconds to 24 hours pnor to washing the pretreated soiled/stamed substrate in conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes.
  • the present invention also encompasses the inclusion of instructions on the use of the particulate solid containing compositions of the present invention with the packages containing the compositions herein or with other forms of advertising associated with the sale or use of the compositions.
  • the instructions may be included in any manner typically used by consumer product manufactunng or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or m advertisements, demonstrations, and/or other wntten or oral instructions which may be connected to the purchase or use of the compositions.
  • the instructions will include a desc ⁇ ption of the use of the composition, for instance, the recommended amount of composition to use m a washing machine to clean the fabnc; the recommended amount of composition to apply to the fabnc; if soaking or rubbing is appropnate .
  • compositions of the present invention are preferably included m a product.
  • the product preferably comp ⁇ ses a composition compnsmg one or more microspheres of the present invention and one or more particulate solids of the present invention, and optionally one or more cleaning adjunct mate ⁇ als, and further comp ⁇ ses instructions for using the product to launder fab ⁇ cs by contacting a fabnc in need of cleaning with an effective amount of the composition such that the composition cleans the fabnc.
  • the following examples are meant to exemplify the microcapsules and detergent compositions of the present invention, but are not necessanly meant to limit or otherwise define the scope of the invention.
  • the following examples are formulations of the polymenc matenal compnsmg the polymenc expandable outer shell of the microspheres in accordance with the present invention. Components are indicated by weight (g).
  • a blowing agent, not identified in the formulation examples, is preferably contained within the cavity of the microspheres.
  • the following examples are formulations of the polymeric material compnsmg the polymenc expandable outer shell of the microspheres in accordance with the present invention. Components are indicated by weight (g).
  • a blowing agent, not identified in the formulation examples, is preferably contained within the cavity of the microspheres.
  • Example 11 The following is a detergent composition in accordance with the present invention.
  • Neodol 23-5 21.5 21.5 21.5 n-BPP 18.5 18.5 18.5
  • Methyl sulfate salt of methyl quaternized polyethoxylated hexamethylenediamine 1.3 1.3 1.3
  • compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are desc ⁇ bed m U.S. 5,691,297 Nassano et al, issued November 11, 1997; U.S. 5,574,005 Welch et al, issued November 12, 1996; U.S. 5,569,645 Dmmwell et al, issued October 29, 1996; U.S. 5,565,422 Del Greco et al, issued October 15, 1996; U.S. 5,516,448 Capeci et al, issued May 14, 1996; U.S. 5,489,392 Capeci et al, issued February 6, 1996; U.S. 5,486,303 Capeci et al, issued January 23, 1996 all of which are incorporated herein by reference.
  • compositions of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are desc ⁇ bed m U.S. 5,679,630 Baeck et al, issued October 21, 1997; U.S. 5,565,145 Watson et al, issued October 15, 1996; U.S. 5,478,489 Fredj et al, issued December 26, 1995; U.S. 5,470,507 Fredj et al, issued November 28, 1995; U.S. 5,466,802 Panandiker et al, issued November 14, 1995; U S. 5,460,752 Fredj et al, issued October 24, 1995; U.S. 5,458,810 Fredj et al, issued October 17, 1995; U.S. 5,458,809 Fredj et al, issued October 17, 1995; U.S. 5,288,431 Huber et al, issued February 22, 1994 all of which are incorporated herein by reference.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions détergentes, en particulier des compositions et/ou des produits détergents pour lessive, tels que des détergents liquides aqueux et/ou non aqueux et/ou en gel et des détergents en granulés et/ou en poudre pour grosses lessives, comprenant une ou plusieurs microsphères possédant une enveloppe polymère extérieure extensible de matériau polymère, soluble dans une solution aqueuse alcaline. Ladite enveloppe définit une cavité contenant des moyens d'extension de la microsphère, de sorte que le volume de ladite cavité augmente. On peut utiliser les microsphères comme particules de charge à faible densité et/ou comme encapsulation renfermant un ou plusieurs ingrédients détergents.
PCT/US2000/011306 1999-04-29 2000-04-27 Microspheres utiles dans des compositions detergentes Ceased WO2000066704A1 (fr)

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AU44945/00A AU4494500A (en) 1999-04-29 2000-04-27 Microspheres useful in detergent compositions

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US13160199P 1999-04-29 1999-04-29
US60/131,601 1999-04-29

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601678B2 (en) 2001-02-07 2009-10-13 Henkel Ag & Co. Kgaa Washing and cleaning agents comprising fine microparticles with cleaning agent components
US7968510B2 (en) 2006-11-22 2011-06-28 The Procter & Gamble Company Benefit agent containing delivery particle
US8242069B2 (en) 2005-06-08 2012-08-14 Firmenich Sa Near anhydrous consumer products comprising fragranced aminoplast capsules
US8940395B2 (en) 2007-06-11 2015-01-27 The Procter & Gamble Company Benefit agent containing delivery particle
CN115121193A (zh) * 2022-07-25 2022-09-30 西安理工大学 荷正电AgO@MgO中空复合微球制备方法

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US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US4828723A (en) * 1987-07-15 1989-05-09 Colgate-Palmolive Company Stable non-aqueous suspension containing organophilic clay and low density filler
US4865773A (en) * 1986-05-21 1989-09-12 In Kim Colloid-active synthetic detergent and process for its manufacture
WO1997038016A1 (fr) * 1996-04-08 1997-10-16 Eastman Chemical Company ESTER DE CELLULOSE MODIFIE ET SENSIBLE AU pH
EP0839902A2 (fr) * 1996-10-31 1998-05-06 Basf Aktiengesellschaft Microcapsules contenant des adjuvants de blanchiment
WO1999001214A1 (fr) * 1997-07-01 1999-01-14 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Encapsulation d'ingredients actifs

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US4865773A (en) * 1986-05-21 1989-09-12 In Kim Colloid-active synthetic detergent and process for its manufacture
US4828723A (en) * 1987-07-15 1989-05-09 Colgate-Palmolive Company Stable non-aqueous suspension containing organophilic clay and low density filler
WO1997038016A1 (fr) * 1996-04-08 1997-10-16 Eastman Chemical Company ESTER DE CELLULOSE MODIFIE ET SENSIBLE AU pH
EP0839902A2 (fr) * 1996-10-31 1998-05-06 Basf Aktiengesellschaft Microcapsules contenant des adjuvants de blanchiment
WO1999001214A1 (fr) * 1997-07-01 1999-01-14 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Encapsulation d'ingredients actifs

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601678B2 (en) 2001-02-07 2009-10-13 Henkel Ag & Co. Kgaa Washing and cleaning agents comprising fine microparticles with cleaning agent components
US8242069B2 (en) 2005-06-08 2012-08-14 Firmenich Sa Near anhydrous consumer products comprising fragranced aminoplast capsules
US7968510B2 (en) 2006-11-22 2011-06-28 The Procter & Gamble Company Benefit agent containing delivery particle
USRE45538E1 (en) 2006-11-22 2015-06-02 The Procter & Gamble Company Benefit agent containing delivery particle
US8940395B2 (en) 2007-06-11 2015-01-27 The Procter & Gamble Company Benefit agent containing delivery particle
US9969961B2 (en) 2007-06-11 2018-05-15 The Procter & Gamble Company Benefit agent containing delivery particle
CN115121193A (zh) * 2022-07-25 2022-09-30 西安理工大学 荷正电AgO@MgO中空复合微球制备方法
CN115121193B (zh) * 2022-07-25 2023-08-08 西安理工大学 荷正电AgO@MgO中空复合微球制备方法

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