WO2000029537A1 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
WO2000029537A1
WO2000029537A1 PCT/US1999/026543 US9926543W WO0029537A1 WO 2000029537 A1 WO2000029537 A1 WO 2000029537A1 US 9926543 W US9926543 W US 9926543W WO 0029537 A1 WO0029537 A1 WO 0029537A1
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WIPO (PCT)
Prior art keywords
donor atoms
organic
ligand
transition
cross
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PCT/US1999/026543
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English (en)
Inventor
Michael Eugene Burns
Andrew Russell Graydon
Regine Labeque
Christopher Mark Perkins
Eugene Steven Sadlowski
Barbara Kay Williams
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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 BR9915319-0A priority Critical patent/BR9915319A/pt
Priority to JP2000582521A priority patent/JP2002530481A/ja
Priority to DE69926390T priority patent/DE69926390T2/de
Priority to EP99957539A priority patent/EP1129164B1/fr
Priority to CA002349011A priority patent/CA2349011A1/fr
Priority to AT99957539T priority patent/ATE300601T1/de
Priority to AU15223/00A priority patent/AU1522300A/en
Publication of WO2000029537A1 publication Critical patent/WO2000029537A1/fr

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    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes

Definitions

  • the present invention relates to bleaching and detergent compositions which comprise a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand
  • the present invention further relates to a method for bleaching/cleaning fab ⁇ c with a catalytically effective amount of said transition-metal bleach catalyst wherein the method is performed substantially free of any organic or inorganic peroxygen compound or precursors to any organic or inorganic peroxygen compound
  • Bleaching of fabric is essentially exposing soiled or stained fab ⁇ c to a chemical reaction the purpose of which is to eliminate the soil or stain.
  • bleaching involved exposure of fab ⁇ c to a solution of hypochlo ⁇ te. Therefore, fabric which was colored or dyed via sensitive pigments were excluded from treatment with bleach.
  • formulators developed various forms of bleach inter aha peroxygen bleaching systems which typically comprise a source of hydrogen peroxide and a bleach activator. This combination of source of hydrogen peroxide and activator plays a dominating role in effective, safe bleaching compositions.
  • An effective example of this peroxygen bleaching system employs perborate
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that bleaching of soils and stains can be accomplished in the absence of a source of hydrogen peroxide or other peroxygen bleaching agent. In other words, it has been surprisingly discovered that effective bleaching of soils and stains can be accomplished solely with a transition-metal bleach catalyst according to the present invention.
  • a first aspect of the present invention relates to bleaching compositions comprising:
  • the present invention further relates to a method for cleaning and/or bleaching soils and stams on fabrics, said method comprising the step of contacting the fabric m need of cleaning and/or bleaching with an aqueous solution containing a composition which is substantially free of a peroxygen source and which comprises: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) the balance earners, fillers, and other adjunct ingredients; provided the concentration of said transition metal bleach catalyst in the aqueous solution is at least about 0.01 ppb and said composition is substantially free of any organic or inorganic peroxygen compounds.
  • compositions and methods of the present invention are suitable for cleaning/bleaching any surface in need of stain removal.
  • hard surface cleaners and automatic dishwashing compositions can employ the bleach catalysts of the present invention in applications which are substantially free of any organic or inorganic peroxygen compounds.
  • the present invention relates to the surprising discovery that bleaching of soils and stains can be accomplished by a transition-metal catalyst in the absence an added peroxygen bleach.
  • Sources of peroxygen bleaches include, but are not limited to. sources of hydrogen peroxide inter alia hydrogen peroxide, percarbonate, perborate. Alkali metal and alkaline earth metal percarbonate and perborate are typically found in laundry bleaching systems. These sources of hydrogen peroxide are typically formulated with one or more bleach activators inter aha nonanoyloxybenzenesulfonate (NOBS), tetraacetylethylenediamme (TAED).
  • NOBS nonanoyloxybenzenesulfonate
  • TAED tetraacetylethylenediamme
  • Bleach activators are typically viewed as precursors to the less stable but more reactive peroxyacid bleaching agents Peroxyacids are formed in situ when the bleach activator (peroxyacid precursor) reacts with hydrogen peroxide or hydroperoxide anion via a perhydrolysis reaction
  • peroxyacids can comprise a peroxygen bleaching system. Although these systems do not have the range of formulatabihty now enjoyed by systems such as NOBS/perborate, nevertheless, suitable methods for formulating peroxyacids inter aha the amido peroxyacid, NAPAA, as described m U S. 5.536.435 Chapman et al., issued July 16, 1996 included herein by reference. Absence of Peroxygen Sources
  • the compositions of the present invention, as well as the methods for cleaning and/or bleaching of fabric which utilize the compositions of the present invention are substantially free of any peroxygen source such as hydrogen peroxide, peroxyacid etc.
  • the compositions of the present invention need only have an effective amount of the herein below described catalyst present for effective bleaching.
  • the term "substantially free” is defined as "the formulator does not include in the composition any peroxygen compound or source of peroxygen at a level required for either effective bleaching without a transition metal catalyst, or which would provide an increase m effectiveness of bleaching in the presence of a transition metal catalyst as defined herein.” Therefore, as will be further described herein below, effective bleaching of stains can be accomplished by simply adding an aqueous or non-aqueous solution of a catalyst as described herein to fab ⁇ c which is stained, preferably the fab ⁇ c is m an aqueous solution when contacted with the catalyst.
  • compositions of the present invention do not require any peroxygen source, but the presence of any minor amounts will not effect the performance of the bleaching compositions described herein.
  • Formulators may typically include a small amount of a source of hydrogen peroxide into compositions for the purposes of stabilizing enzymes, for example, a minor amount of perborate may be added. However, this amount of perborate is typically so minor that it has no effect on the bleaching capacity of the compositions of the present invention. In cases where the formulator has added a minor amount of an oxidant, or other source of peroxide for the purposes of stabilizing an adjunct ingredient, for the purposes of the present invention, those compositions are still defined as "substantially free" of a source of peroxygen as defined herein above if they do not provide additional bleaching activity on stains under typical use conditions.
  • a “substantially free” composition can include an amount of peroxygen source provided the degree to which the catalyst is effective is substantially the same as if the source of peroxygen were absent.
  • any composition which comprises less than 0.1%, preferably less than 0.01% of a primary oxidant, such as a pre-formed peracid or a source of hydrogen peroxide is considered “substantially free” as further defined herein above
  • any laundry liquor, laundry wash water, pre-soak bath, or other fab ⁇ c or surface cleaning solution wherein the present catalysts are used and which comprises less than 0 001% by weight of a source of peroxygen, pre-formed or otherwise formed in situ, is defined herein as "substantially free” as defined herein above.
  • the catalysts of the present invention are used to bleach stains on fabric, or otherwise clean/bleach a hard surface or dishware, and the solution containing the catalyst has a concentration of a source of peroxygen less than 0.001%, that solution is defined herein as "substantially free" of a source of peroxygen.
  • compositions of the present invention comprise an effective amount of a bleach catalyst.
  • an effective amount is defined as "an amount of the transition-metal bleach catalyst present in the present invention compositions, or du ⁇ ng use according to the present invention methods, that is sufficient, under whatever comparative or use conditions are employed, to result in at least partial oxidation of the material sought to be oxidized by the composition or method."
  • the material to be oxidized is an unwanted substance inter alia food and beverage stains, greasy/oily stains, body soils on fabric, however, this is not the limitation to which the invention is applicable. Oxidation m the absence of a source of peroxygen has wide applicability and the present invention is not limited solely to bleaching and/or cleaning of fabric.
  • automatic dishwashing compositions are an embodiment of the present invention wherein bleaching of a stain with a composition and/or with a solution which is "substantially free” of a source of peroxygen is a part of the present invention.
  • hard surface cleaning compositions and solutions which comprise hard surface cleaning compositions which are "substantially free” of a source of peroxygen.
  • the compositions of the present invention comp ⁇ se from about 1 ppb (0.0000001%o), more preferably from about 100 ppb (0.00001%), yet more preferably from about 500 ppb (0.00005%), still more preferably from about 1 ppm (0.0001%) to about 99.9%, more preferably to about 50%. yet more preferably to about 5%, still more preferably to about 500 ppm (0.05%) by weight of the composition, of a transition-metal bleach catalyst as described herein below
  • the transition-metal bleach catalyst of the present invention comprises l) a transition metal selected from the group consisting of Mn(II), Mn(III), Mn(IV),
  • a cross-bridged macropolycyclic ligand being coordinated by four or five donor atoms to the same transition metal, said ligand comprising- a) an organic macrocycle ring containing four or more donor atoms
  • non-donor atoms with a further donor atom preferably selected from the group consisting of H2O, ROH, ⁇ R3, RCN, OH “ , OOH “ , RS “ , RO “ , RCOO “ , OCN “ , SCN “ , N3 “ , CN “ , F “ , Cl “ , Br “ , I “ , O2 “ , NO3 “ , NO2 “ , SOzi 2” , SO3 2” , PO4 3” , organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors such as py ⁇ dines, pyrazines, pyrazoles, lmidazoles, benzimidazoles, py ⁇ midines, t ⁇ azoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted alkyl, optionally substituted alkyl, optionally substituted alkyl, optionally substituted al
  • each E unit represents the moiety having the formula
  • each E unit is a moiety (CR n )t ⁇
  • each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring
  • each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorous, and at least two atoms which comprise D units are bridgehead donor atoms coordinated to the transition metal
  • B units are a carbon atom, a D unit, or a cycloalkyl or heterocychc ring
  • each n is an integer independently selected from 1 and 2, completing the valence of the carbon atoms to which the R units are covalently bonded
  • each G unit is a moiety (CR n )t ⁇
  • each R unit is independently selected from H, alkyl, alkenyl,
  • transition-metal bleach catalysts are the same nomenclature style used in the above-identified references.
  • chemical names of one or more of the herein described hgands . y from the chemical name assigned under the rules of the International Union of Pure and Applied Chemistry (IUPAC).
  • IUPAC International Union of Pure and Applied Chemistry
  • a preferred ligand for the purposes of the present invention 5,12-d ⁇ methyl-l ,5,8, 12- tetraaza-b ⁇ cyclo[6.6.2]hexadecane, has the IUPAC name 4,l l-d ⁇ methyl-l,4,8,l l-tetraaza- b ⁇ cyclo[6.6.2]hexadecane.
  • a further preferred ligand is 5,12-d ⁇ ethyl-l,5,8, 12-tetraaza- b ⁇ cyclo[6.6.2]hexadecane.
  • Transition-metal bleach catalysts useful in the invention compositions can in general include known compounds where they conform with the invention definition, as well as. more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses.
  • Non-limiting examples of suitable catalysts according to the present invention include: D ⁇ chloro-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane Manganese(II) D ⁇ chloro-4, 10-d ⁇ methyl- 1 ,4,7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane Manganese(II) D ⁇ aquo-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate
  • Manganese(IJ) D ⁇ chloro-4,10-d ⁇ methyl-3-phenyl-l,4,7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane
  • Manganese(II) D ⁇ chloro-5, 12-d ⁇ methyl-4,9-d ⁇ phenyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) D ⁇ chloro-4.10-d ⁇ methyl-3 , 8-d ⁇ phenyl- 1 ,4,7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane
  • Manganese(II) D ⁇ chloro-5,12-d ⁇ methyl-2,l l-d ⁇ phenyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) D ⁇ chloro-4,10-d ⁇ methyl-4,9-d ⁇ phenyl-l,4,7,10-tetraazab ⁇ cyclo[5.5.2]tetradecane
  • Manganese(II) D ⁇ chloro-2,4,5,9,l l,12-hexamethyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) D ⁇ chloro-3-butyl-5, 10, 12-t ⁇ methyl-l,5.8, 12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(U) Dichloro- 1,5, 8, 12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) Dichloro- 1,4, 7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane
  • Manganese(II) Dichloro- 1 ,5, 8, 12-tetraazab ⁇ cyclo[6.6.2]hexadecane Iron(II) Dichloro- 1, 4,7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane Iron(II)) Dichloro- 1, 4,7, 10-tetraazab ⁇ cyclo[5.5.2]tetradecane Iron(II)
  • Manganese(U) D ⁇ chloro-5-(T ⁇ methylammomopropyl)dodecyl-12-methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(U) Dichloro- 14,20-d ⁇ methyl- 1,10,14,20-tetraazat ⁇ yclo[8.6.6]docosa-3 (8),4,6-t ⁇ ene
  • Manganese(II) D ⁇ chloro-4,l l-d ⁇ methyl-l,4,7,l l-tetraazab ⁇ cyclo[6.5.2]pentadecane
  • Manganese(II) D ⁇ chloro-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[7.6.2]heptadecane
  • Manganese(H) D ⁇ chloro-5,13-d ⁇ methyl-l,5,9,13-tetraazab ⁇ cyclo[7.7.2]heptadecane
  • Manganese(II) D ⁇ chloro-4,l l-d ⁇ methyl-l,4,7,l l-tetraazab ⁇ cyclo[6.5.2]pentadecane
  • Manganese(II) D ⁇ chloro-5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[7.6.2]heptadecane
  • Manganese(H) D ⁇ ch
  • Manganese(H) D ⁇ aquo-3,10-d ⁇ carboxy-5,12-d ⁇ methyl-l ,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane
  • Manganese(II) Chloro-20-methyl-l ,9,20,24,25-pentaaza-tetracyclo[7.7.7 l ⁇ . l 1 l > ⁇ .]pentacosa-
  • Monometallic, mononuclear complexes are preferred.
  • a monometallic transition-metal bleach catalyst contains only one transition metal atom per mole of complex.
  • a monometallic, mononuclear complex is one m which any donor atoms of the essential macrocyclic ligand are bonded to the same transition metal atom, that is, the essential ligand does not "b ⁇ dge" across two or more transition-metal atoms.
  • manganese transition metal complexes are the manganese(III) and manganese(rV) complexes having the general formula:
  • X is independently a coordinating or bridging species non-limiting examples of which are H 2 0, ⁇ X , O 2" , “ OH, H0 2 " , SH “ , S 2" , >SO, Cl “ , SCN “ , N 3 ⁇ N 3” , RS0 3 “ , RCOO “ , NH 2 " , and NR, wherein R is H alkyl, aryl, each of which is optionally substituted, and R'COO, wherein R 1 is an alkyl, aryl unit, each of which may be optionally substituted; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co- ordmate via all or some of said nitrogen atoms to the manganese centers; z denotes the charge of the complex and is an integer which can have a positive or negative value, Y is a monovalent or multivalent counter-ion, which provides charge neutrality, which dependent upon the charge z of the complex: and
  • these manganese complexes are those wherein said coordinating or bridging group X is either CH 3 COO , O " , and mixtures thereof, preferably when said manganese atom is m the (IV) oxidation state and X is O 2 .
  • Ligands which are preferred are those which contain at least three nitrogen atoms and which coordinate via three nitrogen atoms to one of the manganese centers and are preferably of a macrocyclic nature. Preferred ligands have the formula
  • Non-limitmg examples of preferred ligands are l,4,7-t ⁇ methyl-l ,4,7-t ⁇ azacyclononane
  • Non-hmitmg examples of said counter ions are chloride, sulphate, nitrate, methylsulphate, surfactant-ions, such as long chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates. tosylate, trifluoromethylsulphonate, perchlorate, BPhu , PF 6 , and mixtures thereof.
  • manganese complexes of this type include:
  • manganese complex catalysts are the mononuclear complexes having the formula:
  • LMn IV (OR) 3 wherein manganese, Mn, is in the +4 oxidation state; R is C C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl, and radical combinations thereof; at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese.
  • L is a ligand selected from a C 3 -C 60 radical having at least 3 nitrogen atoms coordinating with the manganese; and Y is an oxidatively-stable counte ⁇ on dependent upon the charge of the complex.
  • Non-limiting examples of preferred complexes are those wherein L is 1.4,7-t ⁇ methyl- 1.4.7-t ⁇ azacyclononane. and 2 methyl-l ,4,7-t ⁇ methyl-l,4,7-t ⁇ azacyclononane. and R is Ci alkyl
  • mononuclear manganese complex catalysts which are capable of bleaching in the absence of a source of hydrogen peroxide or other peroxygen bleaching agent include those having the formula.
  • each X independently represents a coordinating species with the exception of RO , such as Cf . Br . I “ , F " ,
  • the present invention further relates to a method for using the catalysts of the present invention to bleach and/or clean fabric without the requirement of a peroxygen source of peroxygen.
  • the present invention therefore, relates to a method for bleaching soils and stains on fab ⁇ c in the absence of a bleaching agent, said method comp ⁇ smg the step of contacting fab ⁇ c in need of cleaning with an aqueous or non-aqueous solution containing a composition which is substantially free of a peroxygen source, comprising: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) the balance carriers, fillers, and other adjunct ingredients; provided the concentration of said transition metal bleach catalyst in the solution is at least about 0.01 ppb and said composition is substantially free of any organic or inorganic peroxygen compounds.
  • the solution which comprises the transition-metal bleach catalyst has a solution concentration of catalyst of from about 1 ppb, more preferably from about 10 ppb, yet more preferably from about 100 ppb.
  • 100 ppb parts per billion is a solution which comprises 0.00001%o by weight, of a catalyst.
  • solutions which comprises less than 0.001%> of a source of peroxygen are solutions which are "substantially free" of any organic or inorganic peroxygen compounds.
  • Methods directed entirely to large scale bleaching per se, for example, an industrial or manufacturing process may utilized a higher concentration of catalyst, for example, 1 ppm or higher m order to reduce the contact time of the fab ⁇ c with the catalyst containing solution
  • the bleaching, pre-soak, pre-treatment, laundry or automatic diswashing, or hard surface cleaning compositions of the present invention may further comprise one or more carriers and adjunct ingredients.
  • compositions according to the present invention may comprise: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) optionally from about 0.001% to about 90%> by weight, of one or more dye fixing agents; c) optionally from about 0.01% to about 50% by weight, of one or more cellulose reactive dye fixing agents; d) optionally from about 0.01% to about 15% by weight, of a chlorine scavenger, e) optionally about 0.005%) to about 1% by weight, of one or more crystal growth inhibitors; f) optionally from about 0.01% to about 20% by weight, of a fabric abrasion reducing polymer; g) optionally from about 1% to about 12% by weight, of one or more liquid carriers, h) optionally from about 0.001% to about 1% by weight, of an enzyme;
  • the bleaching, pre-soak, pre-treatment, and laundry detergent compositions of the present invention may comprise at least about 0.01% by weight, preferably from about 0.1% to about 60%, preferably to about 30% by weight, of a detersive surfactant system, said system is comprised of one or more category of surfactants depending upon the embodiment, said categories of surfactants are selected from the group consisting of aniomc, catiomc, nonionic, zwitte ⁇ onic, ampholytic surfactants, and mixtures thereof. Within each category of surfactant, more than one type of surfactant of surfactant can be selected. For example, preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1% to 60 %, preferably to about 30%) by weight of the composition.
  • Nonhmiting examples of surfactants useful herein include: a) C ⁇ -Ci 8 alkyl benzene sulfonates (LAS); b) C
  • R' is C5-C31 alkyl
  • R° is selected from the group consisting of hydrogen, C1 -C4 alkyl, C 1 -C4 hydroxyalkyl
  • 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 m a reductive animation reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of -CH 2 (CHOH) n CH 2 OH, -CH(CH 2 OH)(CHOH) n .
  • n is an integer from 3 to 5, inclusive
  • R' is hydrogen or a cyclic or aliphatic monosaccha ⁇ de, which are described in U.S. 5,489,393 Connor et al., issued February 6, 1996. and U S.
  • the bleaching, pre-soak, pre-treatment, and laundry detergent compositions of the present invention can also comprise from about 0.001% to about 100% of one or more (preferably a mixture of two or more) mid-cham branched surfactants, preferably mid-cham branched alkyl alkoxy alcohols having the formula.
  • R- are not all hydrogen and, when z is 1. at least O ⁇ R ' is not hydrogen
  • M is a water soluble cation and may comprises more than one type of cation, for example, a mixture of sodium and potassium
  • the index v is an integer from 0 to 13
  • x is an integer from 0 to 13
  • y is an integer from 0 to 13
  • z is an integer of at least 1
  • provided w + x + y + z is from 8 to 14
  • EO and PO represent ethyleneoxy units and propyleneoxy units having the formula:
  • the index m indicates the average degree of alkoxylation within the mixture of surfactants as such, the index m is at least about 0.01, preferably within the range of from about 0 1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably to about 5.
  • the value of the index m represents a dist ⁇ bution of the average degree of alkoxylation corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m
  • the preferred mid-chain branched surfactants of the present invention which are suitable for use in the surfactant systems of the present invention have the formula:
  • the surfactant systems of the present invention which comprise mid-cham branched surfactants are preferably formulated in two embodiments.
  • a first preferred embodiment comprises mid-cham branched surfactants which are formed from a feedstock which comp ⁇ ses 25%o or less of mid-chain branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-cham branched surfactant component will comprise 25% or less of surfactant molecules which are non-linear surfactants.
  • a second preferred embodiment comprises mid-cham branched surfactants which are formed from a feedstock which comprises from about 25% to about 70% of mid-cham branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-chain branched surfactant component will comprise from about 25%> to about 10% surfactant molecules which are non-linear surfactants.
  • the surfactant systems of the laundry detergent compositions of the present invention can also comprise from about 0 001%, preferably from about 1%, more preferably from about 5%. most preferably from about 10% to about 100%, preferably to about 60%, more preferably to about 30% by weight, of the surfactant system, of one or more (preferably a mixture of two or more) mid-cham branched alkyl arylsulfonate surfactants, preferably surfactants wherein the aryl unit is a benzene ⁇ ng having the formula'
  • L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon atoms
  • R 1 , R 2 , and R 3 are each independently hydrogen or C C 3 alkyl, provided R 1 and R 2 are not attached at the terminus of the L unit
  • M is a water soluble cation having charge q wherein a and b are taken together to satisfy charge neutrality.
  • compositions of the present invention especially when comp ⁇ sing surfactants, preferably comprise one or more detergent builders or builder systems.
  • the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%o, preferably to about 50%, more preferably to about 30%) by weight, of detergent builder.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1%) builder. 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, of the detergent builder Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-contaimng detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tnpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosihcates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates described in U.S. 4,664.839 Rieck, issued May 12, 1987.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Alummosilicate builders are useful in the present invention. Examples of suitable alummosilicate builders are described in U.S. 4,274,975 Corkhill et al. included herein by reference. Alummosilicate 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. Alummosilicate builders include those having the empirical formula:
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide va ⁇ ety 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 m salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • 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 biodegradabihty. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccmates are also especially useful m such compositions and combinations. Dispersants
  • any suitable clay/soil dispersant or anti-redepostion agent can be used m the laundry compositions of the present invention.
  • polymeric dispersing agents which include polymeric polycarboxylates and polyethylene glycols, are suitable for use m the present invention.
  • Polymenc polycarboxylate materials can be prepared by polymerizing or copolyme ⁇ zing suitable unsaturated monomers, preferably m their acid form.
  • Unsaturated monome ⁇ c 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, citracomc acid and methylenemalonic acid
  • the presence m the polymeric polycarboxylates herein or monome ⁇ c segments, containing no carboxylate radicals such as vmylmethyl 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 de ⁇ ved from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polyme ⁇ zed acrylic acid.
  • the average molecular weight of such polymers m 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 m detergent compositions has been disclosed, for example, m Diehl, U.S Patent 3,308,067, issued march 7, 1967.
  • Acryhc/maleic-based copolymers may also be used as a preferred component of the 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, preferably from about 5,000, more preferably from about 7,000 to 100,000, more preferably to 75,000, most preferably 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 m European Patent Application No.
  • Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol te ⁇ olymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acryhc/maleic/vinyl alcohol
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these 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.
  • Soil Release Agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions according to the present invention may optionally comp ⁇ se one or more soil release agents.
  • soil release agents will generally comp ⁇ se from about 0.01%), preferably from about 0.1%, more preferably from about 0.2%> to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition.
  • Polymenc soil release agents are characte ⁇ zed by having both hydrophilic segments, to hydrophilize the surface of hydiophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and, thus, serve as an anchor for the hydrophilic segments.
  • the detergent and cleaning compositions herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include other proteases, amylases, cellulases and hpases.
  • Such matenals are known m the art and are commercially available under such trademarks as . They may be inco ⁇ orated into the non-aqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "prills".
  • Another suitable type of enzyme compnses those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP.” Suitable enzymes and levels of use are described in U.S. Pat. No. 5,576,282, 5,705,464 and 5,710,115.
  • Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein.
  • Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition.
  • Prills in the compositions of the present invention have been found, in compa ⁇ son with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are mco ⁇ orated into aqueous liquid detergents.
  • enzymes added to the compositions herein may be in the form of granulates, preferably T-granulates.
  • "Detersive enzyme" means any enzyme having a cleaning, stam removing or otherwise beneficial effect m a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases
  • Preferred enzymes for laundry pu ⁇ oses include, but are not limited to, proteases, cellulases, hpases and peroxidases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility
  • Suitable enzymes include, but are not limited to. hemicellulases, peroxidases, proteases, cellulases, xylanases, hpases, phosphohpases, esterases, cutmases, pectinases. keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgmnases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases, hyaluronidase, chondroitmase, laccase, and known amylases. or mixtures thereof.
  • the cellulases useful m the present invention include both bacterial or fungal cellulases.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Tnchoderma, Thielavia and Sporot ⁇ chum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.
  • cellulases examples include cellulases produced by a strain of Humicola msolens (Humicola g ⁇ sea var. thermoidea), particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 ammo acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the ammo acid sequence disclosed in WO 91/17243.
  • suitable cellulases are the EGIB cellulases from Tnchoderma longibrachiatum described in WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described m European patent application No. 91202879.2, filed November 6. 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, W096/17994 and W095/24471. Cellulases, when present, are normally mco ⁇ orated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known m the art, and include, for example, horseradish peroxidase, hgnmase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-containmg detergent compositions are disclosed, for example, m U.S. Patent Nos.
  • Enhancers are generally comprised at a level of from 0.1%) to 5% by weight of total composition.
  • Preferred enhancers are substitued phenthiazme and phenoxasme 10- Phenothiazinepropiomcacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10- phenoxazmepropiomc acid (POP) and 10-methylphenoxazme (desc ⁇ bed m WO 94/12621) and substitued sy ⁇ ngates (C3-C5 substitued alkyl synngates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally mco ⁇ orated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • Enzymatic systems may be used as bleaching agents.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • Suitable hpase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutze ⁇ ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable hpases include those which show a positive immunological cross-reaction with the antibody of the hpase, produced by the microorganism Pseudomonas fluorescent LAM 1057 This hpase is available from Amano Pharmaceutical Co.
  • Amano- P Lipase P
  • Other suitable commercial hpases include Amano-CES, hpases ex Chromobacter viscosum, e.g Chromobacter viscosum var lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum hpases from U S. Biochemical Co ⁇ ., U.S.A.
  • hpases ex Pseudomonas gladioli
  • hpases such as Ml n " L ⁇ poma ⁇ R (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • hpolytic enzymes described m EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever
  • cutmases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely hpases which do not require mterfacial activation. Addition of cutmases to cleaning compositions have been described in e g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever)
  • Lipases and/or cutmases when present, are normally mco ⁇ orated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • phosphohpases may be mco ⁇ orated into the cleaning compositions of the present invention.
  • suitable phosphohpases included- EC 3.1.1.32 Phospholipase Al ; EC 3.1.1 4 Phospholipase A2; EC 3.1.1.5 Lysophohpase; EC 3.1.4.3 Phospholipase C; EC 3.1 4.4. Phospo pase D.
  • phosphohpases include LECITASE® from Novo Nordisk A S of Denmark and Phospholipase A2 from Sigma.
  • amylases are also included.
  • the combined action of the phospholipase and amylase provide substantive stam removal, especially on greasy/oily, starchy and highly colored stains and soils.
  • the phospholipase and amylase when present, are mco ⁇ orated into the compositions of the present invention at a pure enzyme weight ratio between 4500: 1 and 1 :5, more preferably between 50: 1 and 1 : 1.
  • Suitable proteases are the subtihsms which are obtained from particular strains of B subtilis and B hcheniformis (subtihsin BPN and BPN')
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243.784 to Novo.
  • Proteolytic enzymes also encompass modified bacterial se ⁇ ne proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and m European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial se ⁇ ne protealytic enzyme which is called “Protease A” herein.
  • Suitable is the protease called herein "Protease C”, which is a variant of an alkaline se ⁇ ne protease from Bacillus in which Lysme replaced arginine at position 27, tyrosme replaced vahne at position 104, se ⁇ ne replaced asparagme at position 123.
  • Protease C is described m EP 90915958.4, corresponding to WO 91/06637, Published May 16, 1991 Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described m WO95/10591, having an ammo acid sequence derived by replacement of a plurality of ammo acid residues replaced m the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilism from Bacillus amyloliquefaciens or to equivalent ammo acid residues m other carbonyl hydrolases or subtihs
  • proteases descnbed in patent applications EP 251 446 and WO 91/06637, protease BLAP® described m WO91/02792 and their va ⁇ ants descnbed in WO 95/23221.
  • protease from Bacillus sp. NCLMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are descnbed in WO 92/03529 A to Novo.
  • a protease having decreased adso ⁇ tion and increased hydrolysis is available as descnbed in WO 95/07791 to Procter & Gamble.
  • a recombmant trypsin-hke protease for detergents suitable herein is descnbed in WO 94/25583 to Novo.
  • Other suitable proteases are descnbed in EP 516 200 by Unilever. Particularly useful proteases are described in PCT publications. WO 95/30010; WO
  • Suitable proteases are commercially available as ESPERASE®,
  • Such proteolytic enzymes when present, are inco ⁇ orated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0 001% to 0.2%, more preferably from 0.005%o to 0 1% pure enzyme by weight of the composition
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains WO94/02597 describes cleaning compositions which mco ⁇ orate mutant amylases. See also W095/ 10603
  • Other amylases known for use m cleaning compositions include both ⁇ - and ⁇ - amylases ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257, EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1.296,839 (Novo).
  • amylases are stability-enhanced amylases described in W094/18314 and WO96/05295, Genencor, and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed m WO 95/10603. Also suitable are amylases described in EP 277 216
  • Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and
  • Termamyl®, Ban® ,Fungamyl® and Duramyl® all available from Novo Nordisk A S Denmark.
  • W095/26397 desc ⁇ bes other suitable amylases : ⁇ -amylases charactensed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°
  • amylolytic enzymes when present, are mco ⁇ orated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024%) to 0.048%> pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Ongm can further be mesophilic or extremophihc (psychrophihc, psychrotrophic, hermophilic, barophihc, alkalophihc, acidophihc, halophihc, etc.). Purified or non-punfied forms of these enzymes may be used.
  • the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the variant may be designed such that the optimal pH. bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.
  • ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility.
  • the isoelectric point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase in isoelectric point may help to improve compatibility with aniomc surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e g. additional salt bridges and enforcing calcium binding sites to increase chelant stability
  • detersive enzymes when present, are normally co ⁇ orated m the cleaning composition at levels from 0.0001%o to 2% of pure enzyme by weight of the cleaning composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • enzyme oxidation scavengers examples include ethoxylated tetraethylene polyammes.
  • Amylase enzymes are suitable for use in the compositions of the present invention.
  • Amylase enzymes and variants used in the present invention include, but are not limited to, the amylase enzymes descnbed in WO 95/26397 and in WO 96/23873 (Novo). These enzymes are mco ⁇ orated into cleaning compositions at a level of from about 0.0001 ), preferably from about 0.00018%), more preferably from about 0.00024%), most preferably from about 0.05% to about 0.1%), preferably to about 0.060%>, more preferably to about 0.048%) by weight of the cleaning compositions of pure enzyme.
  • amylase variants are preferably selected from the group consisting of ⁇ -amylase va ⁇ ants.
  • Suitable ⁇ -amylase variants for use m the present invention include, but are not limited to the following ⁇ -amylases: (i) ⁇ -amylase characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by Phadebas® ⁇ -amylase activity assay and/or;
  • ( ⁇ ) ⁇ -amylase according to (l) comprising the ammo acid sequence shown in SEQ LO NO. 1 or an ⁇ -amylase being at least 80% homologous with the ammo acid sequence shown in SEQ LD No 1 and/or;
  • ⁇ -amylase according to (l) comprising the ammo acid sequence shown in SEQ LD No 2 or an ⁇ -amylase being at least 80% homologous with the ammo acid sequence shown m SEQ LD No. 2 and/or;
  • ⁇ -amylase according to (l) comp ⁇ smg the following ammo acid sequence N- terminal. H ⁇ s-H ⁇ s-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-T ⁇ -Tyr-Leu-Pro-Asn- Asp (SEQ LD No. 3) or an ⁇ -amylase being at least 80%o homologous with the ammo acid sequence shown (SEQ LD No. 3) in the N-termmal and/or;
  • (vn) ⁇ -amylase showing positive lmmunological cross-reactivity with antibodies raised against an ⁇ -amylase having an ammo acid sequence corresponding respectively to SEQ LD No. 1 , LD No. 2, or LD No. 3 and/or;
  • (vin) vanant of a parent ⁇ -amylase wherein the parent ⁇ -amylase (1) has one of the ammo acid sequences shown in SEQ LD No. 1, LD No. 2, or LD No. 4, respectively, or (2) displays at least 80%> homology with one or more of said ammo acid sequences, and/or displays lmmunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said ammo acid sequences, and or is encoded by a DNA sequence which hybndizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said ammo acid sequences, in which variants: (A) at least one ammo acid residue of said parent ⁇ -amylase has been deleted; and or (B) at least one ammo acid residue of said parent ⁇ -amylase has been replaced by a different ammo acid residue; and or (C) at least one ammo acid residue has been inserted relative to said parent ⁇ -a
  • a polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective ammo acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227. 1985, p. 1435, reveals an identity of X%
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in a host organism transformed with the DNA sequence.
  • Enzyme Stabilizers are intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in a host organism transformed with the DNA sequence.
  • Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified m U S 3,600,319, EP 199.405 and EP 200.586 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. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. Nos 5,705,464, 5,710,115 and 5,576,282.
  • N,N'-b ⁇ s(2-am ⁇ noethyl)-l,3-propaned ⁇ amme (5.00g, 31.3 mmol) and absolute ethanol (100 mL).
  • the solution is stirred under argon and cooled to 15°C using an ice bath.
  • Aqueous glyoxal (4.78 g., 33 mmol, 40% m water) is added dropwise with stir ⁇ ng Upon completion of the addition, the solution is concentrated under reduced pressure to yield a clear, colorless oil.
  • the isolated oil has the formula 1.
  • Cyclic amine 1 (6.0 g) is suspended in acetonit ⁇ le (100 mL). Potassium carbonate (25 g) and 1 ,3-propaned ⁇ ol ditosylate (12.61 g, 32.8 mmol) is added. The solution is stirred vigorously at RT overnight. The reaction is then warmed to 70°C and filtered hot with glass fiber filter paper and vacuum filtration. The resulting solid is washed with acetonit ⁇ le (100 mL). The acetonit ⁇ le filtrate is concentrated under reduced pressure to yield a light green oil having the formula 2 :
  • a second crop of product is obtained by further washing of the solid material and subsequent treatment of the resulting solid in a like manner.
  • Total yield is 636 g (93%).
  • the following are non-limiting examples of Heavy Duty Granular (HDG) laundry detergent compositions according to the present invention. TABLE I weight %
  • HDL Heavy Duty Liquid

Abstract

L'invention concerne des compositions détergentes de blanchiment, de pré-trempage, de pré-traitement et de lavage, comprenant: A) une quantité catalytiquement efficace d'un catalyseur de blanchiment à base de métal de transition possédant un complexe métal de transition et un ligand macropolycyclique ponté transversalement, par exemple un chlorure de manganèse 5,12-diméthyl-1,5,8,12-tétra-azabicyclo[6.6.2] héxadécane (II) de formule (1), et B) les excipients et autres constituants adjuvants; pour autant que ladite composition soit sensiblement exempte de composés péroxydes organiques ou inorganiques.
PCT/US1999/026543 1998-11-13 1999-11-09 Compositions de blanchiment WO2000029537A1 (fr)

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BR9915319-0A BR9915319A (pt) 1998-11-13 1999-11-09 Composições alvejantes
JP2000582521A JP2002530481A (ja) 1998-11-13 1999-11-09 ブリーチ組成物
DE69926390T DE69926390T2 (de) 1998-11-13 1999-11-09 Bleichmittelzusammensetzungen
EP99957539A EP1129164B1 (fr) 1998-11-13 1999-11-09 Compositions de blanchiment
CA002349011A CA2349011A1 (fr) 1998-11-13 1999-11-09 Compositions de blanchiment contenant des catalyseurs de blanchiment metallique de transition macropocyclique pontes
AT99957539T ATE300601T1 (de) 1998-11-13 1999-11-09 Bleichmittelzusammensetzungen
AU15223/00A AU1522300A (en) 1998-11-13 1999-11-09 Bleach compositions

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WO2001016271A1 (fr) * 1999-09-01 2001-03-08 Unilever Plc Composition et procede de blanchiment d'un substrat
WO2001016261A2 (fr) * 1999-09-01 2001-03-08 Unilever Plc Composition et procede de blanchiment d'un substrat
US6518231B2 (en) 2000-12-18 2003-02-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Enhancement of air bleaching catalysts
US6551977B2 (en) 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US6569354B2 (en) 1999-12-24 2003-05-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6586383B2 (en) 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
US6617299B1 (en) 1999-04-01 2003-09-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6653271B2 (en) 1999-09-01 2003-11-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6696403B2 (en) 2001-02-05 2004-02-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6720299B2 (en) 2001-02-16 2004-04-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching composition of enhanced stability and a process for making such a composition
US6818149B2 (en) 2000-12-15 2004-11-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Ligand and complex for catalytically bleaching a substrate
US7036176B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Sequential dispensing of laundry additives during automatic machine laundering of fabrics
US7036177B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Dispensing of rinse additives into the rinse cycle during automatic machine laundering of fabrics
US7086110B2 (en) 2002-02-13 2006-08-08 The Procter & Gamble Company Selective dispensing of laundry additives during automatic machine laundering of fabric
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US7501389B2 (en) 2003-10-31 2009-03-10 Conopco Inc. Bispidon-derivated ligands and complexes thereof for catalytically bleaching a substrate
US7534757B2 (en) 2003-10-31 2009-05-19 Conopco Inc. Ligand and complex for catalytically bleaching a substrate
EP2135934A1 (fr) 2008-06-16 2009-12-23 Unilever PLC Utilisation d'une composition de détergent de blanchisserie
US7716956B2 (en) 2002-12-20 2010-05-18 The Procter & Gamble Company Attachment means
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WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2441820A1 (fr) 2010-10-14 2012-04-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Particules de détergent pour le lavage du linge
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
WO2012104159A1 (fr) 2011-01-31 2012-08-09 Unilever Plc Compositions détergentes liquides alcalines
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
EP2522714A1 (fr) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge
EP2522715A1 (fr) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge
WO2012156250A1 (fr) 2011-05-13 2012-11-22 Unilever Plc Compositions de détergent de blanchisserie concentrées aqueuses
WO2013092052A1 (fr) 2011-12-20 2013-06-27 Unilever Plc Détergents liquides isotropes comprenant un polymère détachant
US8492048B2 (en) 2006-07-19 2013-07-23 Acal Energy Limited Fuel cells
WO2013171210A1 (fr) 2012-05-16 2013-11-21 Unilever Plc Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé
US8603684B2 (en) 2007-09-20 2013-12-10 Acal Energy Limited Fuel cells
US8647781B2 (en) 2008-01-23 2014-02-11 Acal Energy Limited Redox fuel cells
US8753783B2 (en) 2006-04-25 2014-06-17 ACAL Enegy Limited Fuel cells with improved resistance to fuel crossover
WO2014114570A1 (fr) 2013-01-23 2014-07-31 Unilever Plc Additif non coloré de lavage du linge destiné à l'amélioration de l'antiredéposition de salissures particulaires
EP2770044A1 (fr) 2013-02-20 2014-08-27 Unilever PLC Gel lamellaire avec un oxyde d'amine
US8951695B2 (en) 2008-01-23 2015-02-10 Acal Energy Limited Redox fuel cell with catholyte redox mediator
US9005828B2 (en) 2006-03-24 2015-04-14 Acal Energy Limited Redox fuel cells with a catholyte solution containing a polyoxometallate
US9029042B2 (en) 2007-09-24 2015-05-12 Acal Energy Limited Redox fuel cell
US9136554B2 (en) 2006-07-19 2015-09-15 Acal Energy Limited Fuel cells
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017198574A1 (fr) 2016-05-17 2017-11-23 Unilever Plc Compositions liquides de détergent pour lessive
WO2017198438A1 (fr) 2016-05-17 2017-11-23 Unilever Plc Compositions détergentes liquides pour le linge
WO2017202923A1 (fr) 2016-05-27 2017-11-30 Unilever Plc Composition de blanchisserie
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
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US7976582B2 (en) * 2007-01-16 2011-07-12 Conopco, Inc. Bleaching of substrates
WO2011150138A1 (fr) * 2010-05-26 2011-12-01 The Procter & Gamble Company Agents encapsulés
CN103174011A (zh) * 2011-11-24 2013-06-26 东华大学 四氮双环十四烷金属配合物在纺织品低温练漂助剂中的应用
CN103194895A (zh) * 2011-11-24 2013-07-10 东华大学 四氮杂环十六烷金属配合物在纺织品低温练漂助剂中的应用
CN103194894A (zh) * 2011-11-24 2013-07-10 东华大学 四吡啶基五氮金属配合物在纺织品低温练漂助剂中的应用

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WO1998039335A1 (fr) * 1997-03-07 1998-09-11 The Procter & Gamble Company Procede ameliore de production de macropolycycles pontes transversalement

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US6617299B1 (en) 1999-04-01 2003-09-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6653271B2 (en) 1999-09-01 2003-11-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
WO2001016261A2 (fr) * 1999-09-01 2001-03-08 Unilever Plc Composition et procede de blanchiment d'un substrat
WO2001016261A3 (fr) * 1999-09-01 2001-08-30 Unilever Plc Composition et procede de blanchiment d'un substrat
WO2001016271A1 (fr) * 1999-09-01 2001-03-08 Unilever Plc Composition et procede de blanchiment d'un substrat
US6569354B2 (en) 1999-12-24 2003-05-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6818149B2 (en) 2000-12-15 2004-11-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Ligand and complex for catalytically bleaching a substrate
US6518231B2 (en) 2000-12-18 2003-02-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Enhancement of air bleaching catalysts
US6696403B2 (en) 2001-02-05 2004-02-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
US6720299B2 (en) 2001-02-16 2004-04-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching composition of enhanced stability and a process for making such a composition
US6586383B2 (en) 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
US6551977B2 (en) 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US7115549B2 (en) 2001-08-02 2006-10-03 Carnegie Mellon University Composition comprising macrocyclic tetra-amido metal complex as bleaching catalyst
US7086110B2 (en) 2002-02-13 2006-08-08 The Procter & Gamble Company Selective dispensing of laundry additives during automatic machine laundering of fabric
US7340790B2 (en) 2002-02-13 2008-03-11 Procter & Gamble Company Universal dispenser for dispensing of laundry additives during automatic machine laundering of fabrics
US7036176B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Sequential dispensing of laundry additives during automatic machine laundering of fabrics
US7036177B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Dispensing of rinse additives into the rinse cycle during automatic machine laundering of fabrics
US7168273B2 (en) 2002-11-07 2007-01-30 The Procter & Gamble Company Selective dispensing apparatus
US7716956B2 (en) 2002-12-20 2010-05-18 The Procter & Gamble Company Attachment means
US7501389B2 (en) 2003-10-31 2009-03-10 Conopco Inc. Bispidon-derivated ligands and complexes thereof for catalytically bleaching a substrate
US7534757B2 (en) 2003-10-31 2009-05-19 Conopco Inc. Ligand and complex for catalytically bleaching a substrate
US7445643B2 (en) 2003-12-03 2008-11-04 The Procter & Gamble Company Automatic machine laundering of fabrics
EP1700907A1 (fr) 2005-03-11 2006-09-13 Unilever N.V. Composition liquide de blanchiment
US9005828B2 (en) 2006-03-24 2015-04-14 Acal Energy Limited Redox fuel cells with a catholyte solution containing a polyoxometallate
US8753783B2 (en) 2006-04-25 2014-06-17 ACAL Enegy Limited Fuel cells with improved resistance to fuel crossover
US9136554B2 (en) 2006-07-19 2015-09-15 Acal Energy Limited Fuel cells
US8492048B2 (en) 2006-07-19 2013-07-23 Acal Energy Limited Fuel cells
US8603684B2 (en) 2007-09-20 2013-12-10 Acal Energy Limited Fuel cells
US9029042B2 (en) 2007-09-24 2015-05-12 Acal Energy Limited Redox fuel cell
US8647781B2 (en) 2008-01-23 2014-02-11 Acal Energy Limited Redox fuel cells
US8951695B2 (en) 2008-01-23 2015-02-10 Acal Energy Limited Redox fuel cell with catholyte redox mediator
EP2135934A1 (fr) 2008-06-16 2009-12-23 Unilever PLC Utilisation d'une composition de détergent de blanchisserie
WO2011120772A1 (fr) 2010-03-31 2011-10-06 Unilever Plc Incorporation de microcapsules dans des détergents liquides structurés
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2441820A1 (fr) 2010-10-14 2012-04-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Particules de détergent pour le lavage du linge
WO2012104159A1 (fr) 2011-01-31 2012-08-09 Unilever Plc Compositions détergentes liquides alcalines
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
WO2012136427A1 (fr) 2011-04-04 2012-10-11 Unilever Plc Procédé de lavage d'un tissu
EP2522714A1 (fr) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge
WO2012156250A1 (fr) 2011-05-13 2012-11-22 Unilever Plc Compositions de détergent de blanchisserie concentrées aqueuses
EP2522715A1 (fr) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Compositions de détergent concentré aqueux pour le linge
WO2013092052A1 (fr) 2011-12-20 2013-06-27 Unilever Plc Détergents liquides isotropes comprenant un polymère détachant
WO2013171210A1 (fr) 2012-05-16 2013-11-21 Unilever Plc Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé
WO2014114570A1 (fr) 2013-01-23 2014-07-31 Unilever Plc Additif non coloré de lavage du linge destiné à l'amélioration de l'antiredéposition de salissures particulaires
EP2770044A1 (fr) 2013-02-20 2014-08-27 Unilever PLC Gel lamellaire avec un oxyde d'amine
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017198574A1 (fr) 2016-05-17 2017-11-23 Unilever Plc Compositions liquides de détergent pour lessive
WO2017198438A1 (fr) 2016-05-17 2017-11-23 Unilever Plc Compositions détergentes liquides pour le linge
WO2017202923A1 (fr) 2016-05-27 2017-11-30 Unilever Plc Composition de blanchisserie
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus

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CA2349011A1 (fr) 2000-05-25
AU1522300A (en) 2000-06-05
EP1129164B1 (fr) 2005-07-27
TR200101330T2 (tr) 2001-10-22
AR021250A1 (es) 2002-07-03
JP2002530481A (ja) 2002-09-17
BR9915319A (pt) 2001-08-07
CN1333813A (zh) 2002-01-30
DE69926390T2 (de) 2006-03-30
DE69926390D1 (de) 2005-09-01
EP1129164A1 (fr) 2001-09-05
ATE300601T1 (de) 2005-08-15

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