WO1997042294A1 - Compositions detergentes comportant des polymeres du type polyamine et des enzymes du type cellulase - Google Patents

Compositions detergentes comportant des polymeres du type polyamine et des enzymes du type cellulase Download PDF

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Publication number
WO1997042294A1
WO1997042294A1 PCT/US1997/007058 US9707058W WO9742294A1 WO 1997042294 A1 WO1997042294 A1 WO 1997042294A1 US 9707058 W US9707058 W US 9707058W WO 9742294 A1 WO9742294 A1 WO 9742294A1
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Prior art keywords
mixtures
units
alkyl
alkylene
formula
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PCT/US1997/007058
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English (en)
Inventor
Rajan Keshav Panandiker
Chanchal Kumar Ghosh
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR9710664A priority Critical patent/BR9710664A/pt
Priority to AU28150/97A priority patent/AU2815097A/en
Priority to EP97922501A priority patent/EP0910618A1/fr
Priority to JP9539970A priority patent/JPH11508320A/ja
Publication of WO1997042294A1 publication Critical patent/WO1997042294A1/fr
Priority to NO985103A priority patent/NO985103L/no

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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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the present invention relates to detergent compositions comprising cellulase enzymes and water soluble and/or dispersible, modified polyamines having functionalized backbone moieties which provide depilling benefits.
  • the cellulase enzymes are present in an amount capable of degrading cellulose.
  • at least about 0.1% by weight ofthe detergent composition is a surfactant.
  • Conventional detergent formulations usually contain surfactants, builders and other additives to improve the removal of soil. It is recognized by those skilled in the art of formulating detergents that enzymes, a unique class of proteins, can be added to conventional detergents to improve the cleaning of fabrics, dishes, and other hard surfaces. Enzymes are substances formed by living cells which catalyze biochemical reactions, and when used in detergent formulations, they enhance the cleaning ability ofthe detergent. Likewise, it is also known to those skilled in the art of laundry detergents that when conventional enzyme-containing laundry detergents are used in the wash process, the surfactant and builder present in the formulation enhance the action ofthe enzyme. Common enzymes included in conventional laundry detergents include: amylase, which breaks down starch; protease, which catalyzes reactions that break down proteins; lipases which work on lipids; and cellulase which breaks down cellulose.
  • Cellulases are known in the art as enzymes that hydrolyze cellulose ( ⁇ -1,4- glucan linkages) to form glucose, cellobiose, cellooligosaccharides, etc.
  • Celluloytic enzymes are recognized by those skilled in the art of detergent formulation not only as agents that enhance the cleaning ability of detergents but also as agents that modify the fabric surface by softening and improving its feel. Repeated washing of cotton-containing fabric can result in the fabric assuming a harsh and unpleasant stiffness and result in pilling. Pilling is the presence of small bundles or "pills" of fibers which gather on cotton fabrics after repeated washings.
  • the use of laundry detergent formulations containing cellulase can reduce or eliminate the stiffness and harshness of fabrics which contain cotton.
  • cellulase enzymes also assist in reducing the pilling effect from repeated washings and assist in maintaining the whiteness of fabrics.
  • cellulase enzymes in laundry detergent compositions are employed as stain removers and contribute to the overall impression of cleaning performance perceived by the consumer.
  • cellulase preparations are complex mixtures of which only a certain fraction is effective as a catalyst in the washing process.
  • certain cellulases can produce negative effects on cotton garments, such as weight loss and tensile strength loss. These negative effects can be minimized by choosing a combination of cellulase with specific detergent components which help to modify the surface of fabrics without the negative effects.
  • soil release polymers typically comprise an oligomeric or polymeric ester "backbone" and are generally very effective on polyester or other synthetic fabrics where the grease or similar hydrophobic stains form an attached film and are not easily removed in an aqueous laundering process.
  • the soil release polymers have a less dramatic effect on "blended” fabrics, that is on fabrics that comprise a mixture of cotton and synthetic material, and have little or no effect on cotton articles.
  • the modified polyamines ofthe present invention are equally effective when the laundry detergent compositions disclosed herein are solid or liquid.
  • the solid laundry detergents may be in the form of granules, flakes or laundry bars.
  • the liquid detergents can have a wide range of viscosity and may include heavy concentrates, pourable "ready" detergents, or light duty fabric pre-treatments.
  • the modified polyamines disclosed in the present method are especially compatible with other laundry detergent additives and adjuncts.
  • an object ofthe present invention to provide laundry detergent compositions that comprise an effective cellulase enzyme together with a water soluble and/or dispersible, modified polyamine fabric surface modifying agents of the present invention.
  • This combination provides a laundry detergent composition that is effective for providing surface modifying benefits, depilling and cleaning benefits to all fabric.
  • U.K. 1,314,897, published April 26, 1973 teaches a hydroxypropyl methyl cellulose material for the prevention of wet-soil redeposition and improving stain release on laundered fabric.
  • U. S. Patent No. 3,897,026 issued to Kearney discloses cellulosic textile materials having improved soil release and stain resistance properties obtained by reaction of an ethylene-maleic anhydride co-polymer with the hydroxyl moieties ofthe cotton polymers.
  • U.S. Patent No. 3,912,681 issued to Dickson teaches a composition for applying a non-permanent soil release finish comprising a polycarboxylate polymer to a cotton fabric.
  • U.S. Patent 4,559,056 issued to Leigh, et alia discloses a process for treating cotton or synthetic fabrics with a composition comprising an organopolysiloxane elastomer, an organosiloxaneoxyalkylene copolymer crosslinking agent and a siloxane curing catalyst. See also U.S. Patent Nos. 4,579,681 and 4,614,519. These disclose vinyl caprolactam materials have their effectiveness limited to polyester fabrics, blends of cotton and polyester, and cotton fabrics rendered hydrophobic by finishing agents.
  • alkoxylated polyamines and quaternized alkoxylated polyamines are disclosed in European Patent Application 206,513 as being suitable for use as soil dispersents, however their possible use as fabric surface modifying agents are not disclosed.
  • these materials do not comprise N-oxides, a key modification made to the polyamines of the present invention and a component of the increased bleach stability exhibited by the presently disclosed compounds.
  • the present invention relates to detergent compositions comprising: a) at least about 0.1 % by weight, of a detersive surfactant; b) at least about 0.001 % by weight, of cellulase enzyme; and c) at least about 0.05%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 7%, by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent, said agent comprising a polyamine backbone corresponding to the formula:
  • W units are backbone units having the formula:
  • Y units are branching units having the formula:
  • backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, dialkylarylene, -(R1O) X R1 -, -(RlO ⁇ R ⁇ OR 1 )*-, - (CH2CH(OR 2 )CH2O)(R 1 O) y -R 1 O(CH 2 CH(OR 2 )CH 2 ) w -, - C(O)(R 4 ) r C(O)-, -CH 2 CH(OR2)CH 2 -, and mixtures thereof; wherein R* is C2-C6 alkylene and mixtures thereof; R 2 is hydrogen, -(R ⁇ B, and mixtures thereof; R 3 is Cj-Ci g alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 ary
  • (CH 2 )pCO 2 M -(CH 2 ) q CH(S ⁇ 3M)CH 2 S ⁇ 3M, - (CH 2 )qCH(SO 2 M)CH2SO3M, -(CH 2 ) p PO 3 M, -PO3M, and mixtures thereof;
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;
  • X is a water soluble anion;
  • m has the value from 4 to about 400;
  • n has the value from 0 to about 200;
  • p has the value from 1 to 6;
  • q has the value from 0 to 6;
  • r has the value of 0 or 1 ;
  • w has the value 0 or 1 ;
  • x has the value from 1 to 100;
  • y has the value from 0 to 100;
  • z has the value 0 or 1.
  • the detergent compositons will further, optionally but preferably, comprises effective amounts of adjunct ingredients selected from builders, optical brighteners, bleaches, bleach boosters, bleach activators, noncellulase enzymes, enzyme activators, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.
  • the present invention comprises detergent compositions especially suitable for use on cotton, non-cotton, or mixtures of cotton and non-cotton fabric
  • the present invention comprises the following formulations.
  • a preferred liquid laundry detergent composition providing fabric modifying benefits comprises: a) at least about 10%, by weight, of a detersive surfactant selected from anionic and nonionic detersive surfactants; b) from about 0.05% to about 2%, by weight, of a cellulase enzyme; and c) from about 0.5% to about 10%, by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent, said agent comprising a polyamine backbone corresponding to the formula:
  • V units are terminal units having the formula:
  • W units are backbone units having the formula:
  • Y units are branching units having the formula:
  • backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C]2 dihydroxy-alkylene, Cg-Cj2 dialkylarylene, -(R ⁇ O) x R ⁇ -, - (R * O) x R5(OR !
  • Rl is C2-C5 alkylene and mixtures thereof;
  • R 2 is hydrogen, -(Rl ⁇ ) x B, and mixtures thereof;
  • R 3 is Cj-C j g alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof;
  • R 4 is C J-C12 alkylene, C4-C12 alkenylene, Cg-Ci2 arylalkylene, C ⁇ -C ⁇ Q arylene, and mixtures thereof;
  • R ⁇ is Cj-C ⁇ alkylene, C3-C]2 hydroxy-alkylene, C4
  • R 6 is C 2 -Ci2 alkylene or Cfr C]2 arylene
  • E units are selected from the group consisting of hydrogen, C j - C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH 2 ) p CO 2 M, -(CH 2 ) q SO 3 M, -CH(CH 2 CO 2 M)-CO2M, -(CH 2 ) p PO3M, - (Rl ⁇ ) x B, -C(O)R3, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, C!-C 6 alkyl, -(CH 2 )
  • a method for laundering and depilling fabrics with pilled fibers comprising contacting said pilled fabrics with an aqueous washing solution formed from an effective amount ofthe detergent composition of this invention.
  • the laundry detergent compositions ofthe present invention comprise the following ingredients.
  • the laundry detergent compositions according to the present invention comprise at least 0.001% by weight, preferably at least about 0.01%. of a cellulase enzyme.
  • an effective amount of cellulase enzyme is sufficient for use in the laundry detergent compositions described herein.
  • the term "an effective amount” refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like.
  • the compositions herein will typically comprise from about 0.05% to about 2%, preferably from about 0.1% to about 1.5% by weight of a commercial enzyme preparation.
  • the cellulase enzymes of the present invention are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • the optimum pH ofthe enzyme-containing composition is between about 7 and about 9.5.
  • suitable cellulases include those produced by a strain of Humicola insolens, Humicola grisea var. thermoidea, and cellulases produced by a species of Bacillus sp. or Aeromonas sp.
  • Other useful cellulases are those extracted from the hepatopancreas ofthe marine mollusc Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in the following: GB 2,075,028 A (Novo Industri A/S); GB 2,095,275 A (Kao Soap Co., Ltd.); and Horikoshi et al, U.S. Patent No. 3,844,890 (Rikagaku Kenkyusho).
  • suitable cellulases and methods for their preparation are described in PCT International Publication Number WO 91/17243, published November 14, 1991 , by Novo Nordisk A/S.
  • Cellulases are known in the art and can be obtained from suppliers under the tradenames: Celluzyme®, Endolase®, and Carezyme®.
  • Modified Polyamine Polymers are water-soluble or dispersible, modified polyamines. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree. In general, the polyamine backbones described herein are modified in such a manner that each nitrogen ofthe polyamine chain is thereafter described in terms of a unit that is substituted, quatemized, oxidized, or combinations thereof.
  • modification is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution), quatemizing a backbone nitrogen (quatemized) or oxidizing a backbone nitrogen to the N-oxide (oxidized).
  • substitution and “substitution” are used interchangably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit. Quaternization or oxidation may take place in some circumstances without substitution, but substitution preferably is accompanied by oxidation or quaternization of at least one backbone nitrogen.
  • linear or non-cyclic polyamine backbones that comprise the fabric surface modifying agents ofthe present invention have the general formula:
  • primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units.
  • V or Z "terminal" units For example, when a primary amine moiety, located at the end ofthe main polyamine backbone or branching chain having the structure
  • H 2 N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
  • V terminal unit
  • some or all ofthe primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain “terminal” units.
  • a primary amine moiety located at the end ofthe main polyamine backbone having the structure
  • -NH 2 is modified according to the present invention, it is thereafter defined as a Z "terminal” unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
  • secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone” units.
  • W backbone
  • H — [N-R]- is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit.
  • W backbone
  • some or all ofthe secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone” units.
  • tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
  • Y branch point of either the polyamine backbone or other branching chains or rings, having the structure
  • I —[N-R]- is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit.
  • some or ail or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain “branching" units.
  • the R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
  • the polyamine backbone has the formula
  • the polyamine backbones ofthe present invention comprise no rings.
  • a fully non-branched linear modified polyamine according to the present invention has the formula
  • VW m Z that is, n is equal to 0.
  • n the lower the ratio of m to n
  • m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value ofthe index n is very low or nearly 0, are also preferred.
  • Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quatemized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y units for the pu ⁇ oses ofthe present invention.
  • Modified primary amine moieties are defined as V "terminal" units having one of three forms: a) simple substituted units having the structure: E-N-R —
  • Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure:
  • Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure: — N-R—
  • Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms: a) simple substituted units having the structure:
  • a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH 2 CH 2 )HN-.
  • the Z "terminal” unit derives from a terminal primary amino moiety ofthe structure -NH2.
  • Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
  • the Z "terminal” unit can be substituted with any ofthe E units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be a hydrogen.
  • the polyamines ofthe present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms ofthe backbone.
  • R units comprise units that for the purposes ofthe present invention are referred to as “hydrocarbyl R” units and "oxy R” units.
  • the "hydrocarbyl" R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two ofthe carbon atoms ofthe R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; Cg-Cj2 dialkylarylene which for the pu ⁇ ose ofthe present invention are arylene moieties having two alkyl substituent groups as part ofthe linking chain.
  • a dialkylarylene unit has the formula
  • the unit need not be 1 ,4-substituted, but can also be 1,2 or 1,3 substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene.
  • the "oxy" R units comprise -(Rl O) x R5(ORl ) x -, CH2CH(OR 2 )CH2O) z (R 1 O) y Rl(OCH 2 CH(OR 2 )CH2)w- 5 -CH2CH(OR2)CH 2 -, -(R!O) x Rl-, and mixtures thereof.
  • R units are C2-C12 alkylene, C3-C j 2 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-Ci 2 dialkylarylene, -(R1 O) X R1-, -CH 2 CH(OR 2 )CH 2 -, -(CH 2 CH(OH)CH 2 O) z (R * 0) y R ] (OCH 2 CH-(OH)CH 2 ) w -, -(R I O) X R5(OR1) X -, more preferred R units are C2-C12 alkylene, C3-C12 hydroxy ⁇ alkylene, C4-C12 dihydroxyalkylene, -(Rl ⁇ ) ⁇ R 1 -, -(R ⁇ xR ⁇ OR 1 ) ⁇ , -(CH 2 CH(OH)CH2 ⁇ ) z (R 1 O) y R 1 (OCH2CH-(OH)CH2)w-- and mixtures thereof, even more preferred R units are C2-C2-
  • Rl units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
  • R 2 is hydrogen, and -(R*O) x B, preferably hydrogen.
  • R3 is Cj-Cjg alkyl, C7-C 12 arylalkylene, C7-C 12 alkyl substituted aryl, C ⁇ - C12 aryl, and mixtures thereof , preferably Cj-C 12 alkyl, C7-C12 arylalkylene, more preferably C1-C12 alkyl, most preferably methyl.
  • R) units serve as part of E units described herein below.
  • R 4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-Ci2 arylalkylene, Cg-CjQ arylene, preferably Cj-Cio alkylene, Cg-Ci2 arylalkylene, more preferably C2-Cg alkylene, most preferably ethylene or butylene.
  • R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,
  • R 5 is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
  • (OH)CH 2 - more preferably -CH 2 CH(OH)CH 2 -.
  • R" is C2-C12 alkylene or Cg-C ⁇ arylene.
  • the preferred "oxy" R units are further defined in terms ofthe R ⁇ , R 2 , and R ⁇ units.
  • Preferred "oxy" R units comprise the preferred R*, R 2 , and R ⁇ units.
  • the preferred surface modifying agents ofthe present invention comprise at least 50% Rl units that are ethylene. Preferred Rl, R 2 , and R ⁇ units are combined with the "oxy" R units to yield the preferred "oxy” R units in the following manner.
  • E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3- C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2) p CO 2 M, - (CH 2 ) q SO 3 M, -CH(CH 2 CO 2 M)CO2M, -(CH 2 ) p PO 3 M, -(Rl ⁇ ) m B, -C(O)R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C1-C22 alkylene, - (R ⁇ OJmB, -C(O)R 3 , -(CH 2 ) p CO 2 M, -(CH 2 ) q SO 3 M, -CH(CH 2 CO2M)C0 2 M, more
  • E units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides.
  • the backbone chain or branching chains do not comprise units ofthe following structure:
  • E units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N- oxides.
  • the E unit -C(O)R 3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure
  • B is hydrogen, C ⁇ -C 6 alkyl, -(CH 2 )qSO 3 M, -(CH 2 ) p CO2M, -(CH2) q - (CHSO3M)CH2SO3M, -(CH2) q (CHSO 2 M)CH 2 SO3M, -(CH 2 ) p PO3M, -PO 3 M, preferably hydrogen, -(CH2) q SO 3 M, -(CH2) q (CHSO3M)CH 2 SO3M, -(CH2) q - (CHSO2M)CH2SO3M, more preferably hydrogen or -(CH2) q SO3M.
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
  • a sodium cation equally satisfies -(CH2) p CO2M, and -(CH2) q S03M, thereby resulting in -(CH2) p CO2Na, and -(CH 2 ) q SO3Na moieties.
  • More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
  • more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical.
  • a -(CH2) p PO3M moiety substituted with sodium atoms has the formula -(CH2) p PO3Na3.
  • Divalent cations such as calcium (Ca 2+ ) or magnesium (Mg 2+ ) may be substituted for or combined with other suitable mono-valent water soluble cations.
  • Preferred cations are sodium and potassium, more preferred is sodium.
  • X is a water soluble anion such as chlorine (Cl"), bromine (Br) and iodine (T) or X can be any negatively charged radical such as sulfate (SO4 2 -) and methosulfate (CH3SO3-).
  • indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1 ; w has the value 0 or 1 , x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1 ; m has the value from 4 to about 400, n has the value from 0 to about 200; m + n has the value of at least 5.
  • the preferred modified polyamine surface modifying agents ofthe present invention comprise polyamine backbones wherein less than about 50% ofthe R groups comprise "oxy" R units, preferably less than about 20% , more preferably less than 5%, most preferably the R units comprise no "oxy" R units.
  • the most preferred agents which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% ofthe R groups comprise more than 3 carbon atoms.
  • ethylene, 1 ,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
  • the surface modifying agents ofthe present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less ofthe -NH units are modified.
  • the term "homogeneous polyamine backbone” is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact ofthe chosen method of chemical synthesis.
  • ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator” would be considered to comprise a homogeneous polyamine backbone for the purposes ofthe present invention.
  • a polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone.
  • a polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless ofthe degree of branching or the number of cyclic branches present.
  • non-homogeneous polymer backbone refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
  • a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1 ,2-propylene units.
  • a mixture of "hydrocarbyl” and “oxy” R units is not necessary to provide a non-homogeneous backbone. The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity ofthe polyamine agents of the present invention.
  • Preferred polymers ofthe present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quatemized amines, nitrogens totally or partially oxidized to N- oxides, and mixtures thereof.
  • polyethyleneoxy moieties totally or partially quatemized amines
  • nitrogens totally or partially oxidized to N- oxides, and mixtures thereof.
  • not all backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs ofthe formulator.
  • the degree of ethoxylation is also determined by the specific requirements ofthe formulator.
  • the preferred polyamines that comprise the backbone ofthe compounds ofthe present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's.
  • a common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethylenimines (PEI's).
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4: 1, however PEI's having a ratio of m to n of about 2: 1 are most preferred.
  • Preferred backbones, prior to modification have the general formula: [H 2 NCH 2 CH 2 ] n -[NCH 2 CH 2 ] m -[NCH 2 CH 2 ]n-NH 2 wherein m and n are the same as defined herein above.
  • Preferred PEI's, prior to modification will have a molecular weight greater than about 200 daltons.
  • the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom ofthe polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
  • polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich 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; all herein inco ⁇ orated by reference.
  • Formula I depicts a polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, having the formula
  • Formula I This is an example of a polymer that is fully modified by one type of moiety.
  • Formula II depicts a polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said agent having the formula
  • Formula II Formula III depicts a polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quatemized.
  • the substituents are polyoxyalkyleneoxy units, -(CH2CH2 ⁇ )7H, or methyl groups.
  • the modified PEI polymer has the formula
  • Formula III depicts a polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH2CH2 ⁇ )7H or methyl), quatemized, oxidized to N-oxides or combinations thereof.
  • the resulting polymer has the formula
  • not all nitrogens of a unit class comprise the same modification.
  • the present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides.
  • This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion ofthe primary amine nitrogens with one or more substituents prior to oxidation or quaternization. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
  • Detersive surfactants In addition to preferred anionic and nonionic detersive surfactants described herein above, other detersive surfactants that are suitable for use in the present invention are cationic, ampholytic, zwitterionic, and mixtures thereof, further described herein below.
  • compositions of the present invention comprise at least about 0.1%, preferably at least 1%, more preferably at least 10%, most preferably from about 5% to about 80% by weight, of an anionic detersive surfactant.
  • Alkyl sulfate surfactants either primary or secondary, are a type of anionic surfactant of importance for use herein.
  • Alkyl sulfates have the general formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl straight or branched chain or hydroxyalkyl having a C 10-C20 alkyl component, more preferably a C12-C1 g alkyl or hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali metal cation (e.g., sodium potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like.
  • alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g., below about 50
  • Alkyl alkoxylated sulfate surfactants are another category of preferred anionic surfactant. These surfactants are water soluble salts or acids typically ofthe formula RO(A) m SO3M wherein R is an unsubstituted C 10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C ⁇ -Cjg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is hydrogen or a water soluble cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substiruted-ammonium cation.
  • R is an unsubstituted C 10-C24 alkyl or hydroxyalkyl group having
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines, e.g., monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C ⁇ Cjg alkyl polyethoxylate (1.0) sulfate, C]2-C ⁇ g alkyl polyethoxylate (2.25) sulfate, Ci2-C ⁇ g alkyl polyethoxylate (3.0) sulfate, and Ci2-C ⁇ g alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • compositions ofthe present invention may comprise at least about 0.1%, preferably at least 1%, more preferably at least about 10%, most preferably from about 5% to about 80% by weight, of an nonionic detersive surfactant.
  • Preferred nonionic surfactants such as C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of C ⁇ to C12 alkyl phenols, alkylene oxide condensates of Cg-C22 alkanols and ethylene oxide/propylene oxide block polymers (PluronicTM-BASF Co ⁇ .), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions.
  • AE C12-C18 alkyl ethoxylates
  • AE C12-C18 alkyl ethoxylates
  • C6-C12 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
  • Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado (inco ⁇ orated herein by reference) are also preferred nonionic surfactants in the compositions ofthe invention.
  • nonionic surfactants are the polyhydroxy fatty acid amides having the formula: wherein Rl is C5-C31 alkyl, preferably straight chain C7-C 19 alkyl or alkenyl, more preferably straight chain C9-C 17 alkyl or alkenyl, most preferably straight chain C ⁇ ⁇ - Cj5 alkyl or alkenyl, or mixtures thereof; R& is selected from the group consisting of hydrogen, C1 -C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl.
  • Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof.
  • Preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose com syrup, high fructose com syrup, and high maltose com syrup can be utilized as well as the individual sugars listed above.
  • Q is more preferably selected from the group consisting of -CH 2 (CHOH) n CH 2 OH, -CH(CH 2 OH)(CHOH) n . ⁇ CH 2 OH, -
  • n is an integer from 3 to 5, inclusive
  • R' is hydrogen or a cyclic or aliphatic monosaccharide.
  • Most preferred substituents for the Q moiety are glycityls wherein n is 4, particularly -CH2(CHOH)4CH2OH.
  • R 7 CO -N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or 2-hydroxy propyl.
  • Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • a particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-methyl glucomide, a compound ofthe above formula wherein R' is alkyl (preferably C ⁇ ⁇ -C ⁇ 3), R ⁇ , is methyl and Q is 1-deoxyglucityl.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C JO-C I S N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C1 g glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ n-C]6 soaps may be used.
  • Other conventional useful surfactants are listed in standard texts.
  • other detersive surfactants, described herein below may be used in the laundry detergent compositions.
  • Nonlimiting examples of other surfactants useful herein typically at levels from about 1% to about 55%, by weight include the conventional C ⁇ j -Cjg alkyl benzene sulfonates ("LAS"), the Cjo-Cjg secondary (2,3) alkyl sulfates ofthe formula CH 3 (CH2) x (CHOSO3 ⁇ M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 " M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, Cio-Cjg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the CiQ-18 glycerol ethers, the Cio-Cjg alkyl polyglycosides and their corresponding sulfated polyglycoside
  • the conventional nonionic and amphoteric surfactants such as the Ci2-C ⁇ g alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy /propoxy), C ⁇ -Cjg betaines and sulfobetaines ("sultaines"), CjQ-Cig amine oxides, and the like, can also be included in the overall compositions.
  • the CjQ-Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C j o-C ] g N-(3-methoxypropyl) glucamide. C ⁇ 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • anionic surfactants useful for detersive pu ⁇ oses can also be included in the compositions hereof. These can include salts (including, for example, sodium potassium, ammonium, and substituted ammonium salts such a mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, Cg-C22 primary or secondary alkanesulphonates, Cg-C24 olefinsulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succina
  • the laundry detergent compositions according to the present invention comprise adjunct ingredients and carriers, said adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, noncellulase enzymes, enzyme activators, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof, and mixtures thereof, however this list is not meant to be exhaustive or to exclude any suitable material used by the formulator.
  • SRA ADJUNCT INGREDIENTS Non-cotton Soil Release Agent
  • SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, ofthe compositions. Preferred SRA's are described herein above.
  • SRA's suitable for the compositions ofthe present invention typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • SRA's can include a variety of charged, e.g., anionic or even cationic species, see U.S. 4,956,447, issued September 1 1, 1990 to Gosselink, et al., as well as noncharged monomer units, and their structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
  • SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • SRA's include the nonionic end-capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. 4,71 1,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5- sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the Ci -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., CJ-C6 vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.
  • Another SRA is an oligomer having empirical formula (CAP) 2 (EG/PG) 5 (T)5(SIP) ⁇ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy- 1 ,2-propyleneoxy units in a defined ratio, preferably about 0.5: 1 to about 10: 1, and two end-cap units derived from sodium 2-(2- hydroxyethoxy)-ethanesulfonate.
  • CAP empirical formula
  • Said SRA preferably further comprises from 0.5% to 20%, by weight ofthe oligomer, of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
  • Suitable monomers for the above SRA include Na-2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals ofthe polymer through an ester ofthe isolated carboxylic acid of trimellitic anhydride rather than by opening ofthe anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate- based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; (IV) poly( vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate. including both nonionic and cationic polymers, see U.S.
  • Still other classes include: (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989 and 4,525,524.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will be at levels of from about 0.05% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to about 20%, ofthe detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any ofthe bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning pu ⁇ oses that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) ofthe peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those ofthe formulae: R!N(R5)C(O)R 2 C(O)L or RlC(O)N(R 5 )R 2 C(O)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence ofthe nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators ofthe above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, inco ⁇ orated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, inco ⁇ orated herein by reference.
  • a highly preferred activator ofthe benzoxazin- type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams ofthe formulae:
  • R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, inco ⁇ orated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,1 14,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mnl ⁇ r 2( u "0)3(l,4,7-trimethyl-l,4,7-triazacyclo- nonane)2(PF6)2, MnHl2( u " ⁇ )l( u "OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million ofthe active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the CjQ-Cig alkanolamides can be inco ⁇ orated into the compositions, typically at 1%-10% levels.
  • the C 10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C ⁇ 3.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerin, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1, preferably between about 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0.
  • Laundry products are typically at pH 9-1 1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • Enzymes - Noncellulase enzymes can be included in the present detergent compositions for a variety of pu ⁇ oses, including removal of protein- based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles or dishes, for the prevention of refugee dye transfer, for example in laundering, and for fabric restoration.
  • Suitable other enzymes include proteases, amylases, lipases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Preferred enzymes for laundry pu ⁇ oses include, but are not limited to, proteases, lipases and peroxidases.
  • Enzymes are normally inco ⁇ orated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram ofthe detergent composition.
  • the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
  • Amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 1 1, June 1985, pp 6518-6521.
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase. Stability can be measured using any ofthe art- disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more ofthe Baccillus amylases, especialy the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb.
  • particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®.
  • Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms ofthe Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their inco ⁇ oration into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • 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 described in GB 1,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adso ⁇ tion and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially preferred protease is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, + 135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • Prefe ⁇ ed laundry detergent compositions ofthe present invention may optionally comprise a protease enzyme, referred to as "Protease D", which is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • protease enzyme referred to as "
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303,761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A” herein, Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.
  • subtilisin enzymes in particular BPN', that have been modified by mutating the various nucleotide sequences that code for the enzyme, thereby modifying the amino acid sequence ofthe enzyme.
  • modified subtilisin enzymes have decreased adso ⁇ tion to and increased hydrolysis of an insoluble substrate as compared to the wild-type subtilisin.
  • mutant genes encoding for such BPN' variants are also suitable.
  • Preferred BPN' variants comprise wild-type amino acid sequence wherein the wild-type amino acid sequence at one or more of positions 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 21 1, 212, 213, 214, 215, 216, 218, 219 or 220 is substituted; wherein the BPN' variant has decreased adso ⁇ tion to, and increased hydrolysis of, an insoluble substrate as compared to the wild-type subtilisin BPN'.
  • the positions having a substituted amino acid are 199, 200, 201, 202, 205, 207, 208, 209, 210, 21 1, 212, or 215; more preferably, 200, 201, 202, 205 or 207.
  • Preferred protease enzymes for use according to the present invention also include the subtilisin 309 variants. These protease enzymes include several classes of subtilisin 309 variants.
  • subtilisin 309 variants have a modified amino acid sequence of subtilisin 309 wild-type amino acid sequence, wherein the modified amino acid sequence comprises a substitution at one or more of positions 193, 194, 195, 196, 197, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 21 1, 212, 213 or 214; whereby the subtilisin 309 variant has decreased adso ⁇ tion to, and increased hydrolysis of, an insoluble substrate as compared to the wild-type subtilisin 309.
  • these proteases have amino acids substituted at 193, 194, 195, 196, 199, 201, 202, 203, 204, 205, 206 or 209; more preferably 194, 195, 196, 199 or 200.
  • subtilisin 309 variants may also be a modified amino acid sequence of subtilisin 309 wild-type amino acid sequence, wherein the modified amino acid sequence comprises a substitution at one or more positions in one or more ofthe first, second, third, fourth, or fifth loop regions; whereby the subtilisin 309 variant has decreased adso ⁇ tion to, and increased hydrolysis of, an insoluble substrate as compared to the wild-type subtilisin 309.
  • substitutions at positions other than the loop regions - may be made at positions other than positions in the loop regions, for example, at position 74. If the additional substitution to the subtilisin 309 is mad at position 74 alone, the substitution is preferably with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro, preferably His or Asp. However modifications can be made to one or more loop positions as well as position 74, for example residues 97, 99, 101, 102, 105 and 121.
  • Enzyme Stabilizing System - Enzyme-containing including but not limited to, liquid compositions, herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form ofthe detergent composition.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes inco ⁇ orated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts co ⁇ esponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in- use is sometimes problematic.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • special enzyme inhibition systems can be inco ⁇ orated such that different enzymes have maximum compatibility.
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment ofthe invention; even then, the scavenger is added only for optimum results.
  • the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients, if used.
  • ammonium salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use ofthe composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, ofthe detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function su ⁇ risingly well even in the presence ofthe 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.
  • silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 mo ⁇ hology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O2 x +i -y ⁇ O 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 herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 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 crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Aiuminosilicate builders are useful in the present invention. Aiuminosilicate 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. Aiuminosilicate builders include those having the empirical formula:
  • 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.
  • aiuminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amo ⁇ hous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aiuminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aiuminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aiuminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aiuminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the pu ⁇ oses ofthe present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
  • Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric 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. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (prefe ⁇ ed), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the prefe ⁇ ed builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., Cj2-C ⁇ g monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1,1 -diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions ofthe invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Prefe ⁇ ed, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Prefe ⁇ ed compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight ofthe detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.
  • compositions ofthe present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight ofthe water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most prefe ⁇ ed soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 11 1,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of prefe ⁇ ed antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalomc acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water- soluble salts of polymerized 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 materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a prefe ⁇ ed component ofthe dispersing/anti-redeposition agent.
  • Such materials 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 materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol te ⁇ olymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acrylic/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 pu ⁇ oses range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHOR WHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[ 1 ,2-d]triazoles; 4,4'-bis- ( 1 ,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(- venzimidazol-2-yl)ethylene; 1 ,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2- yl)thiophene; 2-stryl-napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2- d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are prefe ⁇ ed herein.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ g-C4Q ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a prefe ⁇ ed category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Another prefe ⁇ ed category of non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO j /2 units and to Si ⁇ 2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (prefe ⁇ ed), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1 , preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorgano
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the prefe ⁇ ed solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Prefe ⁇ ed is a weight ratio of between about 1 : 1 and 1:10, most preferably between 1 :3 and 1 :6, of polyethylene glycolxopolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC LI 01.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2- alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,1 18 and EP 150,872.
  • the secondary alcohols include the Cg-Cjg alkyl alcohols having a Cj-C ⁇ chain.
  • a prefe ⁇ ed alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to about 5%, by weight, ofthe detergent composition.
  • from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, ofthe detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, ofthe composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight ofthe finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concu ⁇ ently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • compositions ofthe present invention may also include one or more additional materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl py ⁇ olidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpy ⁇ olidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight ofthe composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • Prefe ⁇ ed polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, py ⁇ ole, imidazole, py ⁇ olidine, piperidine and derivatives thereof
  • the N-O group can be represented by the following general structures:
  • R ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen ofthe N-O group can be attached or form part of any ofthe aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more prefe ⁇ ed pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1 : 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization.
  • the average molecular weight is within the range of 500 to 1,000,000; more prefe ⁇ ed 1,000 to 500,000; most prefe ⁇ ed 5,000 to 100,000.
  • This prefe ⁇ ed class of materials can be refe ⁇ ed to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
  • Copolymers of N-vinylpy ⁇ olidone and N-vinylimidazole polymers are also prefe ⁇ ed for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpy ⁇ olidone from 1 : 1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpy ⁇ olidone (“PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, inco ⁇ orated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • the hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt- forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the prefe ⁇ ed hydrophilic optical brightener useful in the detergent compositions herein.
  • Rj is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • R ⁇ is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA- GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context ofthe present invention.
  • An effective amount ofthe liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
  • potassium hydroxide pellets (Baker, 0.30g, 0.0053 mol). After the potassium hydroxide dissolves, ethylene oxide is added as described above until a weight gain of 60g (co ⁇ esponding to a total of 4.2 ethoxy units) is obtained. A 53g portion of this brown viscous liquid is saved. Ethylene oxide is added to the remaining material as described above until a weight gain of 35.9g (corresponding to a total of 7.1 ethoxy units) is obtained to afford 94.9g of dark brown liquid. The potassium hydroxide in the latter two samples is neutralized by adding the theoretical amounts of methanesulfonic acid.
  • Dimethyl sulfate 28.3g, 0.224 mol is added in one portion to the rapidly stirring solution, which is then stoppered and sti ⁇ ed at room temperature overnight.
  • acetonitrile is removed by rotary evaporation at about 60°C, followed by further stripping of solvent using a Kugelrohr apparatus at approximately 80°C to afford
  • the 1 3 c-NMR (D2O) spectrum obtained on a sample ofthe reaction product indicates the absence of a carbon resonance at ⁇ 58ppm co ⁇ esponding to dimethyl sulfate.
  • the 1 H-NMR (D2O) spectrum shows a partial shifting ofthe resonance at about 2.5 ppm for methylenes adjacent to unquaternized nitrogen has shifted to approximately 3.0 ppm. This is consistent with the desired quaternization of about
  • PEI- 1800, E7 polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen
  • hydrogen peroxide 120 g of a 30 wt % solution in water, 1.06 mol
  • the resonances ascribed to methylene protons adjacent to unoxidized nitrogens have shifted from the original position at -2.5 ppm to -3.5 ppm.
  • To the reaction solution is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for approximately 3 days. The solution is tested and found to be negative for peroxide by indicator paper.
  • the material as obtained is suitably stored as a 51.1% active solution in water.
  • polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) and then further modified by quaternization to approximately 38% with dimethyl sulfate (130 g, -0.20 mol oxidizeable nitrogen, prepared as in Example II), hydrogen peroxide (48 g of a 30 wt % solution in water, 0.423 mol), and water (-50 g).
  • the flask is stoppered, and after an initial exotherm the solution is sti ⁇ ed at room temperature overnight.
  • ⁇ -NMR (D2O) spectrum obtained on a sample taken from the reaction mixture indicates complete conversion ofthe resonances attributed to the methylene peaks previously observed in the range of 2.5-3.0 ppm to a material having methylenes with a chemical shift of approximately 3.7 ppm.
  • To the reaction solution is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for approximately 3 days. The solution is tested and found to be negative for peroxide by indicator paper.
  • the desired material with -38% of the nitrogens quatemized and 62% ofthe nitrogens oxidized to amine oxide is obtained and is suitably stored as a 44.9% active solution in water.
  • polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) subsequently quatemized with dimethyl sulfate to approximately 4.7% (121.7 g, -0.32 mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution in water, 0.588 mol), and water (109.4 g).
  • PEI 1800 E7 polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) subsequently quatemized with dimethyl sulfate to approximately 4.7% (121.7 g, -0.32 mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution in water, 0.588 mol), and water (109.4 g).
  • the flask is stoppered, and after an initial exotherm the solution is sti
  • polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 (224g, 0.637 mol nitrogen) and acetonitrile (150g, 3.65 mol).
  • Dimethyl sulfate (3.8g, 0.030 mol) is added in one portion to the rapidly stirring solution, which is stoppered and sti ⁇ ed at room temperature overnight.
  • the acetonitrile is removed by rotary evaporation at approximately 60°C.
  • the last traces of solvent are removed by further stripping on a Kugelrohr at ⁇ 80°C to afford ⁇ 220g of the desired material obtained as a dark brown viscous liquid in which -4.7% of the nitrogen are quatemized.
  • the 13 C- NMR (D2O) spectrum indicates the consumption of dimethyl sulfate by the absence of a resonance at ⁇ 58ppm.
  • the ⁇ -NMR (D2O) spectrum shows a partial shifting of the resonance at 2.5 ppm (methylene units adjacent to unquatemized nitrogens) to -3.0 ppm.
  • Minors - includes optical brightener and enzymes (protease, lipase, cellulase, and amylase). 3. Polymer according to Example 4.
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, protease, lipase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaC ⁇ 3, talc, silicates, etc.
  • Balance to 100% can, for example, include minors like perfume, suds suppresser, soil dispersant, protease, lipase, amylase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaC ⁇ 3, talc, silicates, etc.

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Abstract

L'invention porte sur une composition détergente comportant des enzymes du type cellulase et des polyamines modifiées hydrosolubles et/ou hydrodispersibles présentant des fragments de squelette fonctionnalisés à effet antiboulochage. Lesdites enzymes sont présentes en une quantité capable de dégrader la cellulose. En outre, au moins environ 0,1 % en poids de la composition consiste en un tensio-actif.
PCT/US1997/007058 1996-05-03 1997-04-25 Compositions detergentes comportant des polymeres du type polyamine et des enzymes du type cellulase WO1997042294A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9710664A BR9710664A (pt) 1996-05-03 1997-04-25 Composi-Æo de detergente compreendendo pol¡meros de poliamina modificada e enzimas de celulase
AU28150/97A AU2815097A (en) 1996-05-03 1997-04-25 Detergent compositions comprising modified polyamine polymers and cellulase enzymes
EP97922501A EP0910618A1 (fr) 1996-05-03 1997-04-25 Compositions detergentes comportant des polymeres du type polyamine et des enzymes du type cellulase
JP9539970A JPH11508320A (ja) 1996-05-03 1997-04-25 修飾ポリアミンポリマーおよびセルラーゼ酵素を含んだ洗剤組成物
NO985103A NO985103L (no) 1996-05-03 1998-11-02 Detergentsammensetninger omfattende modifiserte polyaminpolymerer og cellulase-enzymer

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US1652896P 1996-05-03 1996-05-03
US60/016,528 1996-05-03

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WO1997042294A1 true WO1997042294A1 (fr) 1997-11-13

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CA (1) CA2252853A1 (fr)
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Publication number Priority date Publication date Assignee Title
WO1999042551A1 (fr) * 1998-02-20 1999-08-26 The Procter & Gamble Company Compositions detergentes de blanchiment contenant des polymeres de polyamine modifies
WO2000066696A1 (fr) * 1999-04-29 2000-11-09 Genencor International, Inc. Matrice detergente a base de cellulase
WO2009066987A2 (fr) * 2007-11-22 2009-05-28 Mimos Berhad Appareil d'analyse des nutriments d'un sol
WO2013170002A1 (fr) * 2012-05-11 2013-11-14 The Procter & Gamble Company Composition détergente liquide pour un meilleur lustre
WO2013170001A1 (fr) * 2012-05-11 2013-11-14 The Procter & Gamble Company Composition détergente liquide pour un meilleur lustre
EP2300586B1 (fr) 2008-06-16 2015-04-08 Unilever PLC Perfectionnements relatifs au nettoyage de tissus
US9464261B2 (en) 2010-05-14 2016-10-11 The Sun Products Corporation Polymer-containing cleaning compositions and methods of production and use thereof
WO2016195834A1 (fr) 2015-06-05 2016-12-08 Illinois Tool Works Inc. Détergent pour lessive à usage industriel
EP1876227B2 (fr) † 2006-07-07 2020-08-12 The Procter and Gamble Company Compositions de lavage
EP3862412A1 (fr) * 2020-02-04 2021-08-11 The Procter & Gamble Company Composition de détergent
WO2022199418A1 (fr) * 2021-03-26 2022-09-29 Novozymes A/S Composition détergente à teneur en polymère réduite

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EP0269169A2 (fr) * 1986-11-21 1988-06-01 The Procter & Gamble Company Compositions détergentes contenant de la cellulose
US4891160A (en) * 1982-12-23 1990-01-02 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
EP0581751A1 (fr) * 1992-07-15 1994-02-02 The Procter & Gamble Company Compositions détergentes pour éviter le transfert de colorant contenant des enzymes
WO1995032272A1 (fr) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions de dispersion des salissures a base de polymeres du type polyalkyleneamine ethoxylee/propoxylee
JPH07316590A (ja) * 1994-05-26 1995-12-05 Lion Corp 色移り・再汚染防止剤および洗剤組成物

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EP0269169A2 (fr) * 1986-11-21 1988-06-01 The Procter & Gamble Company Compositions détergentes contenant de la cellulose
EP0581751A1 (fr) * 1992-07-15 1994-02-02 The Procter & Gamble Company Compositions détergentes pour éviter le transfert de colorant contenant des enzymes
WO1995032272A1 (fr) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions de dispersion des salissures a base de polymeres du type polyalkyleneamine ethoxylee/propoxylee
JPH07316590A (ja) * 1994-05-26 1995-12-05 Lion Corp 色移り・再汚染防止剤および洗剤組成物

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999042551A1 (fr) * 1998-02-20 1999-08-26 The Procter & Gamble Company Compositions detergentes de blanchiment contenant des polymeres de polyamine modifies
WO2000066696A1 (fr) * 1999-04-29 2000-11-09 Genencor International, Inc. Matrice detergente a base de cellulase
EP1876227B2 (fr) † 2006-07-07 2020-08-12 The Procter and Gamble Company Compositions de lavage
WO2009066987A2 (fr) * 2007-11-22 2009-05-28 Mimos Berhad Appareil d'analyse des nutriments d'un sol
WO2009066987A3 (fr) * 2007-11-22 2009-10-15 Mimos Berhad Appareil d'analyse des nutriments d'un sol
EP2300586B1 (fr) 2008-06-16 2015-04-08 Unilever PLC Perfectionnements relatifs au nettoyage de tissus
US9464261B2 (en) 2010-05-14 2016-10-11 The Sun Products Corporation Polymer-containing cleaning compositions and methods of production and use thereof
WO2013170002A1 (fr) * 2012-05-11 2013-11-14 The Procter & Gamble Company Composition détergente liquide pour un meilleur lustre
WO2013170001A1 (fr) * 2012-05-11 2013-11-14 The Procter & Gamble Company Composition détergente liquide pour un meilleur lustre
US8623806B2 (en) 2012-05-11 2014-01-07 The Procter & Gamble Company Liquid detergent composition for improved shine
US8759271B2 (en) 2012-05-11 2014-06-24 The Procter & Gamble Company Liquid detergent composition for improved shine
WO2016195834A1 (fr) 2015-06-05 2016-12-08 Illinois Tool Works Inc. Détergent pour lessive à usage industriel
EP3303539A4 (fr) * 2015-06-05 2019-01-23 Illinois Tool Works Inc. Détergent pour lessive à usage industriel
AU2016271153B2 (en) * 2015-06-05 2020-12-24 Illinois Tool Works Inc. Heavy duty laundry detergent
EP3988635A1 (fr) * 2015-06-05 2022-04-27 Illinois Tool Works, Inc. Détergent pour lessive à usage industriel
EP3862412A1 (fr) * 2020-02-04 2021-08-11 The Procter & Gamble Company Composition de détergent
WO2021158429A1 (fr) * 2020-02-04 2021-08-12 The Procter & Gamble Company Composition détergente
CN115023488A (zh) * 2020-02-04 2022-09-06 宝洁公司 洗涤剂组合物
US11859156B2 (en) 2020-02-04 2024-01-02 The Procter & Gamble Company Detergent composition
WO2022199418A1 (fr) * 2021-03-26 2022-09-29 Novozymes A/S Composition détergente à teneur en polymère réduite

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TR199802222T2 (xx) 1999-02-22
ZA973762B (en) 1997-12-04
NO985103L (no) 1999-01-04
HUP9904292A2 (hu) 2000-04-28
CZ354898A3 (cs) 1999-03-17
EP0910618A1 (fr) 1999-04-28
BR9710664A (pt) 1999-08-17
NO985103D0 (no) 1998-11-02
CA2252853A1 (fr) 1997-11-13
MA24163A1 (fr) 1997-12-31
JPH11508320A (ja) 1999-07-21
AR006953A1 (es) 1999-09-29
AU2815097A (en) 1997-11-26

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