WO1999019445A1 - Tensioactifs ramifies en milieu de chaine avec derives cellulosiques - Google Patents

Tensioactifs ramifies en milieu de chaine avec derives cellulosiques Download PDF

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Publication number
WO1999019445A1
WO1999019445A1 PCT/US1997/018841 US9718841W WO9919445A1 WO 1999019445 A1 WO1999019445 A1 WO 1999019445A1 US 9718841 W US9718841 W US 9718841W WO 9919445 A1 WO9919445 A1 WO 9919445A1
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Prior art keywords
integer
alkyl
chain
sulfate
methyl
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PCT/US1997/018841
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English (en)
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Rinko Katsuda
Eriko Kawasaki
Susumu Murata
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The Procter & Gamble Company
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Priority to JP50062599A priority Critical patent/JP3308548B2/ja
Priority to US09/529,261 priority patent/US6242406B1/en
Priority to AU50821/98A priority patent/AU5082198A/en
Priority to CA002305330A priority patent/CA2305330A1/fr
Priority to PCT/US1997/018841 priority patent/WO1999019445A1/fr
Priority to BR9714877-6A priority patent/BR9714877A/pt
Priority to EP97913694A priority patent/EP1021510A1/fr
Publication of WO1999019445A1 publication Critical patent/WO1999019445A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the present invention relates to detergent compositions comprising a select amount of a cellulose derivative and mid-chain branched surfactants.
  • Such mid-chain branched surfactants are mixtures of longer alkyl chain mid-chain branched surfactants derived from mid-chain branched primary alkyl hydrophobic groups and selected hydrophilic groups, said mixtures comprising mid-chain branched primary alkyl hydrophobic groups having an average of greater than 14.5 carbon atoms, preferably greater than about 15 carbon atoms, with preferred surfactants herein being mid-chain branched primary alkyl sulfate surfactants and mid-chain branched primary alkyl alkoxylated sulfate surfactants.
  • the present invention relates to a combination of cellulose derivatives and mixtures of mid-chain branched surfactants which are useful in laundry and cleaning compositions, especially granular and liquid detergent compositions.
  • Conventional detersive surfactants comprise molecules having a water-solubilizing substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group).
  • Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkaryl hydrophobe usually containing from about 10 to about 20 carbon atoms. Accordingly, the manufacturer of such surfactants must have access to a source of hydrophobe groups to which the desired hydrophile can be attached by chemical means.
  • hydrophobe groups comprised the natural fats ' and oils, which were converted into soaps (i.e., carboxylate hydrophile) by saponification with base.
  • soaps i.e., carboxylate hydrophile
  • coconut oil and palm oil are still used to manufacture soap, as well as to manufacture the alkyl sulfate ("AS") class of surfactants.
  • Other hydrophobes are available from petrochemicals, including alkylated benzene which is used to manufacture alkyl benzene sulfonate surfactants ("LAS").
  • LAS alkylated benzene which is used to manufacture alkyl benzene sulfonate surfactants
  • the literature asserts that certain branched hydrophobes can be used to advantage in the manufacture of alkyl sulfate detersive surfactants; see, for example, U.S.
  • alkyl sulfates are well known to those skilled in the art of detersive surfactants. Alkyl sulfates were developed as a functional improvement over traditional soap surfactants and have been found to possess improved solubility and surfactant characteristics. Linear alkyl sulfates are the most commonly used of the alkyl sulfate surfactants and are the easiest to obtain. For example, long-chain linear alkyl sulfates, such as tallow alkyl sulfate, have been used in laundry detergents. However, these have significant cleaning performance limitations, especially with the trend to lower wash temperatures.
  • Z is, for example, OS03Na.
  • Branched Guerbet types are likewise 2-position branched, but also have additional branching substitution, as in:
  • Z is, for example, OS03Na.
  • surfactants which include C12 and C13 alkyl sulfates containing 3 and 4 methyl branches, respectively (see especially p. 32).
  • Known alkyl sulfates also include:
  • Primary alkyl sulfates derived from "Neodol” or “Dobanol” process alcohols these are Oxo products of linear internal olefins or are Oxo products of linear alpha-olefins.
  • the olefins are derived by ethylene oligomerization to form alpha-olefins which are used directly or are isomerized to internal olefins and metathesized to give internal olefins of differering chain-lengths;
  • Primary or Secondary alkyl sulfates other than of linear primary type for example phytol, farnesol, isolated from natural product sources.
  • (I) is a "linear” alkyl sulfate.
  • (I) is also a “primary” alkyl sulfate, in contrast with (VII) which is a “secondary” alkyl sulfate.
  • (II) is also a “primary” alkyl sulfate - but it is “branched”. The branching is exclusively in the "2-position” as in the so-called “linear Guerbet” alkyl sulfates: carbon-counting by convention starts with C1 , which is the carbon atom covalently attached to the sulfate moiety.
  • (Ill) can be used to represent any one of a series of branched alkyl sulfates which, when e is an integer having the value 1 or greater, have only "non-2-position branching".
  • the hydrocarbon portion needs to have at least 12 carbon atoms, preferably more, to acquire good detergency.
  • the indices a,b,c,d,e,f,g,h,i,j,k,l,m,n,o,p,q can, in principle, be adjusted to accommodate this need.
  • Compound (VIII) is the alkyl sulfate derived from a naturally occurring branched alcohol, phytol.
  • Compound (IX) is a highly branched alkyl sulfate, which can, for example, be made by sulfating an alcohol derived from dimerizing isobutylene and performing an Oxo reaction on the product.
  • Compound (XI) is a "neo" alkyl sulfate.
  • (XII) and (XIII) are substructures depicting "vicinal” (XII) and “geminal” or “gem” (XIII) dimethyl branching, respectively.
  • Such substructures can, in principle, occur in alkyl sulfates and other surfactants.
  • Conventional alkyl sulfates can, moreover, be either saturated or unsaturated.
  • Sodium oleyl sulfate for example, is an unsaturated alkyl sulfate.
  • Unsaturated alkyl sulfates such as oleyl sulfate can be relatively expensive and/or relatively incompatible with detergent formulations, especially those containing bleach.
  • complex, highly branched primary alkyl sulfate mixtures having quaternary carbon atoms in the hydrophobe are producible, for example by sulfation of Oxo alcohol made via acid-catalyzed polygas reaction, moreover stereoisome ⁇ sm, possible in many branched alkyl sulfates, further multiplies the number of species, and commercial alkyl sulfates can contain impurities including the corresponding alcohols, inorganic salts such as sodium sulfate, hydrocarbons, and cyclic byproducts of their synthesis
  • sodium isostearyl sulfate which is a mixture of methyl and/or ethyl branches distributed along an otherwise linear alkyl backbone wherein the total number of carbons in the entire molecule are about 18
  • This isostearyl "mixture" is prepared in low yield from natural source feedstocks (i e tall oil, soy, etc ) via a process which results in branching which occurs in an uncontrolled manner, and which can vary depending upon the source of the feedstock EP 401 ,462, assigned to Henkel, published December 12, 1990 describes certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as “sodium isostearyl sulfate” (CAS 34481-82-8, sometimes referred to as "sodium isooctadecyl sulfate”)
  • the preferred long-chain alkyl sulfate compositions containing mid-chain branching are the combination of two or more of these mid-chain branched primary alkyl sulfate surfactants which provide a surfactant mixture that is higher in surfactancy and has better low temperature water solubility than any single branched alkyl sulfate
  • the mixtures as produced comprise the mid-chain branching desirable for use in surfactant mixtures and can be formulated by mixing the desired amounts of individual mid-chain branched surfactants
  • Such superior mixtures are not limited to combinations with other mid-chain branched surfactants but (preferably) they can be suitably combined with one or more other traditional detergent surfactants (e g , other primary alkyl sulfates, linear alkyl benzene sulfonates, alkyl ethoxylated sulfates, nonionic surfactants, etc ) to provide improved surfactant systems
  • Suitable product mixtures can be obtained from processes which utilize fossil-fuel sources (The terms "derived from fossil fuels” or “fossil- fuel de ⁇ ved” herein are used to distinguish coal, natural gas, petroleum oil and other petrochemical derived, "synthetic" surfactants from those derived from living natural resources such as livestock or plants such as coconut palms)
  • One such process is designed to provide branched reaction products which are primarily (85%, or greater) alpha-olefins, and which are then converted into hydrophobes in an Oxo- reaction sequence
  • branched alpha-olefins contain from about 11 to about 18 (avg ) total carbon atoms and comprise a linear chain having an average length in the 10-18 region
  • the branching is predominantly mono-methyl, but some di-methyl and some ethyl branching may occur
  • such process results in little (1%, or less) geminal branching, i e , little, if any, "quaternary" carbon substitution.
  • little (less than about 20%) vicinal branching occurs. Of course, some (ca.
  • this process provides alpha-olefins with: an average number of branches (longest chain basis) in the 0.4-2.5 range; of the branched material, there are essentially no branches on carbons 1 , 2 or on the terminal (omega) carbon of the longest chain of the branched material.
  • the feedstock is subjected to an Oxo carbonylation process.
  • a catalyst e.g., conventional cobalt carbonyl
  • This avoids the formation of vinylidene intermediates (which ultimately yield less favorable surfactants) and allows the carbonylation to proceed at the #1 and #2 carbon atoms.
  • detergent compositions comprising a select amount of a cellulose derivative in combination with long-chain alkyl chain, mid-chain branching surfactant compounds provide cleaning compositions having one or more advantages, including greater surfactancy at low use temperatures, increased resistance to water hardness, greater efficacy in surfactant systems, improved removal of greasy or body soils from fabrics, improved compatibility with detergent enzymes, and the like.
  • the combination of the mid-chain branched surfactant with a select amount of a cellulose derivative unexpectedly provides whiteness maintenance benefits as well as improved soil release from fabrics, particularly cotton fabrics.
  • EP 684,300 published by Lever November 29, 1995, describe beta-branched alkyl sulfates.
  • EP 439,316 describes certain laundry detergents containing a specific commercial
  • C14/C15 branched primary alkyl sulfate namely LIAL 145 sulfate. This is believed to have 61% branching in the 2-position; 30% of this involves branching with a hydrocarbon chain having four or more carbon atoms.
  • U.S. 3,480,556 describes mixtures of from 10 to 90 parts of a straight chain primary alkyl sulfate and from 90 to 10 parts of a beta branched (2-position branched) primary
  • EP 342,917 A Unilever, published Nov. 23, 1989 describes laundry detergents containing a surfactant system in which the major anionic surfactant is an alkyl sulfate having an assertedly "wide range" of alkyl chain lengths (the experimental appears to involve mixing coconut and tallow chain length surfactants).
  • Methyl- substituted sulfates include the known "isostearyl" sulfates; these are typically mixtures of isomeric sulfates having a total of 18 carbon atoms.
  • isostearyl sulfates
  • EP 401 ,462 A assigned to Henkel, published December 12, 1990, describes certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as sodium isostearyl sulfate. See also K.R. Wormuth and S. Zushma, Langmuir, Vol.
  • pp 31-34 relating to foaming data for surfactants which include C12 and C13 alkyl sulfates containing 3 and 4 methyl branches, respectively
  • Varadaraj et al. Langmuir, Vol. 6 (1990), pp 1376-1378 (which describes the micropolarity of aqueous micellar solutions of surfactants including branched alkyl sulfates).
  • Linear Guerbet alcohols are available from Henkel, e.g., EUTANOL G-16.
  • the present invention encompasses detergent compositions, for example those useful for laundering fabrics, washing dishes, or cleaning hard surfaces, comprising:
  • the longer alkyl chain, mid-chain branched surfactant compounds in (a) are of the formula:
  • a D is a hydrophobic C9 to C22 (total carbons in the moiety), preferably from about C12 to about C18, mid-chain branched alkyl moiety having: (1) a longest linear carbon chain attached to the - X - B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C-
  • compositions wherein in the above formula the A ⁇ moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).
  • Preferred detergent surfactant compositions herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A D moiety is a branched primary alkyl moiety having the formula:
  • R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided R, R 1 , and R 2 are not all hydrogen and, when z is 0, at least R or R " * is not hydrogen; w 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 from 0 to 13; and w + x + y + z is from 7 to 13. '
  • surfactant compositions herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A D moiety is a branched primary alkyl moiety having the formula selected from:
  • the present invention relates to detergent compositions comprising a select amount of a cellulose derivative and a longer alkyl chain, mid-chain branched surfactant compounds as described herein.
  • Other detergent surfactants in addition to the mid-chain branched surfactant may be included, but is not required as a part of the detergent composition.
  • a Mid-chain branched surfactants in addition to the mid-chain branched surfactant may be included, but is not required as a part of the detergent composition.
  • mid-chain branched surfactant compositions certain points of branching (e.g., the location along the chain of the R, R 1 , and/or R 2 moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant.
  • the formula below illustrates the mid- chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A b moieties.
  • the detergent surfactant compositions may comprise one or more, preferably two or more mid-chain branched primary alkyl sulfate surfactants having the formula
  • the surfactant mixtures comprise molecules having a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 18.
  • the surfactant mixtures comprise at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 18.
  • a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, R and/or R 2 ) whereby total number of carbon atoms in the molecule is at least 16.
  • the C16 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units.
  • R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R 1 , and R 2 are not all hydrogen. Further, when z is 1 , at least R or R is not hydrogen.
  • the surfactant compositions for the above formula do not include molecules wherein the units R, R "1 , and R 2 are all hydrogen (i.e., linear non-branched primary alkyl sulfates), it is to be recognized that the surfactant compositions may still further comprise some amount of linear, non-branched primary alkyl sulfate. Further, this linear non-branched primary alkyl sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite one or more mid-chain branched primary alkyl sulfates, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkyl sulfate may be admixed into the final product formulation.
  • non-sulfated mid-chain branched alcohol may comprise some amount of the mid-chain branched surfactant compositions. Such materials may be present as the result of incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkyl sulfate surfactant.
  • M is hydrogen or a salt forming cation depending upon the method of synthesis.
  • salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula
  • R 3 , R 4 , R 5 and R ⁇ are independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, C-
  • Preferred cations are ammonium (R 3 , R 4 , R 5 and R ⁇ equal hydrogen), sodium, potassium, mono- , di-, and trialkanol ammonium, and mixtures thereof.
  • the monoalkanol ammonium compounds have R 3 equal to C-
  • Preferred alkanol ammonium salts are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
  • M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium.
  • the preferred surfactant mixtures to be used in the present invention have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more branched primary alkyl sulfates having the formula
  • the mixtures of surfactant comprise at least 5% of a mid chain branched primary alkyl sulfate having R 1 and R 2 independently hydrogen, methyl, provided R 1 and R 2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2. More preferably the mixtures of surfactant comprise at least 20% of a mid chain branched primary alkyl sulfate having R 1 and R 2 independently hydrogen, methyl, provided R 1 and R 2 are not both hydrogen; x + y is equal to 8,9, or 10 and z is at least 2.
  • Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl sulfate surfactants, said mixture comprising at least about 5 % by weight of two or more mid-chain branched alkyl sulfates having the formula:
  • mid-chain branched surfactant composition may comprise a mixture of branched primary alkyl sulfates having the formula
  • R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl, provided R, R-', and R 2 are not all hydrogen;
  • M is a water soluble cation;
  • w 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 ;
  • w + x + y + z is from 8 to 14; provided that when R 2 is a C1-C3 alkyl the ratio of surfactants having z equal to 1 to surfactants having z of 2 or greater is at least about 1 :1 , preferably at least about 1 :5, more preferably at least about 1:10, and most preferably
  • surfactant compositions when R 2 is a C-1-C3 alkyl, comprising less than about 20%, preferably less than 10%, more preferably less than 5%, most preferably less than 1%, of branched primary alkyl sulfates having the above formula wherein z equals 1.
  • Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11 -methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecano
  • Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2, 3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2, 5-methyl tetradecanol sulfate, 2, 6-methyl tetradecanol sulfate, 2, 7-methyl tetradecanol sulfate, 2, 8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl tetradecanol sulfate, 2,11 -methyl tetradecanol sulfate, 2, 12-methyl tetradecanol sulfate, 2, 3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2, 5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol
  • branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants:
  • M is preferably sodium
  • branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants: 2,5-dimethylpentadecylsulfate having the formula:
  • M is preferably sodium
  • the branched surfactant compositions may comprise one or more mid-chain branched primary alkyl polyoxyalkylene surfactants having the formula
  • the surfactant mixtures comprise molecules having a linear primary polyoxyalkylene chain backbone (i.e., the longest linear carbon chain which includes the alkoxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 18.
  • the surfactant mixtures comprise at least one polyoxyalkylene compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 18.
  • a C16 total carbon (in the alkyl chain) primary polyoxyalkylene surfactant having 15 carbon atoms in the backbone must have a methyl branching unit (either R, R 1 or R 2 is methyl) whereby the total number of carbon atoms in the molecule is 16.
  • R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C-1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R 1 , and R 2 are not all hydrogen. Further, when z is 1 , at least R or R 1 is not hydrogen.
  • the surfactant compositions of the above formula does not include molecules wherein the units R, R 1 , and R 2 are all hydrogen (i.e., linear non-branched primary polyoxyalkylenes), it is to be recognized that the surfactant compositions may still further comprise some amount of linear, non-branched primary polyoxyalkylene. Further, this linear non-branched primary polyoxyalkylene surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite mid-chain branched primary polyoxyalkylenes, or for purposes of formulating detergent compositions some amount of linear non-branched primary polyoxyalkylene may be admixed into the final product formulation.
  • non-alkoxylated mid-chain branched alcohol may comprise some amount of the polyoxyalkylene-containing compositions. Such materials may be present as the result of incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched polyoxyalkylene surfactant.
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, more preferably ethoxy, wherein m is at least about 1 , preferably within the range of from about 3 to about 30, more preferably from about 5 to about 20, and most preferably from about 5 to about 15.
  • the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) 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 surfactant mixtures have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl polyoxyalkylenes having the formula
  • the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl polyoxyalkylene having R 1 and R 2 independently hydrogen or methyl, provided R 1 and R 2 are not both hydrogen, x + y is equal to 8, 9 or 10 and z is at least 2
  • Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0 001% to about 99% of a mixture of mid-chain branched primary alkyl polyoxyalkylene surfactants, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl polyoxyalkylenes having the formula
  • the surfactant composition may comprise a mixture of branched primary alkyl polyoxyalkylenes having the formula
  • R, R 1 , and R 2 are each independently selected from hydrogen and C-J-C3 alkyl, provided R, R 1 , and R 2 are not all hydrogen, w 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 , w + x + y + z ⁇ s from 8 to 14, EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 1 ,
  • Preferred mono-methyl branched primary alkyl ethoxylates are selected from the group consisting of 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol ethoxylate, 5-methyl pentadecanol ethoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl pentadecanol ethoxylate, 8- methyl pentadecanol ethoxylate, 9-methyl pentadecanol ethoxylate, 10-methyl pentadecanol ethoxylate, 11-methyl pentadecanol ethoxylate, 12-methyl pentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-methyl hexadecanol ethoxylate, 4-methyi hexadecanol ethoxylate, 5- methyl hexadecanol ethoxylate, 6-methyl hex
  • Preferred di-methyl branched primary alkyl ethoxylates selected from the group consisting of: 2, 3-methyl tetradecanol ethoxylate, 2,4-methyl tetradecanol ethoxylate, 2, 5-methyl tetradecanol ethoxylate, 2,6-methyl tetradecanol ethoxylate, 2, 7-methyl tetradecanol ethoxylate, 2, 8-methyl tetradecanol ethoxylate, 2,9-methyl tetradecanol ethoxylate, 2,10-methyl tetradecanol ethoxylate, 2,11-methyl tetradecanol ethoxylate, 2, 12-methyl tetradecanol ethoxylate, 2, 3-methyl pentadecanol ethoxylate, 2,4-methyl pentadecanol ethoxylate, 2, 5-methyl pentadecanol ethoxylate, 2,6-methyl pentadecanol
  • the branched surfactant compositions may comprise one or more (preferably a mixture of two or more) mid-chain branched primary alkyl alkoxylated sulfates having the formula:
  • the surfactant mixtures comprise molecules having a linear primary alkoxylated sulfate chain backbone (i.e., the longest linear carbon chain which includes the alkoxy-sulfated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 18.
  • the mixtures comprise at least one alkoxylated sulfate compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 18.
  • a C16 total carbon (in the alkyl chain) primary alkyl alkoxylated sulfate surfactant having 15 carbon atoms in the backbone must have a methyl branching unit (either R, R "1 or R 2 is methyl) whereby the total number of carbon atoms in the primary alkyl moiety of the molecule is 16.
  • R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R 1 , and R 2 are not all hydrogen. Further, when z is 1 , at least R or R 1 is not hydrogen.
  • surfactant compositions of the above formula do not include molecules wherein the units R, R 1 , and R 2 are all hydrogen (i.e., linear non-branched primary alkoxylated sulfates), it is to be recognized that surfactant compositions may still further comprise some amount of linear, non-branched primary alkoxylated sulfate. Further, this linear non-branched primary alkoxylated sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite mid-chain branched primary alkoxylated sulfates, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkoxylated sulfate may be admixed into the final product formulation.
  • mid-chain branched alkyl sulfate may be present in the compositions. This is typically the result of sulfation of non-alkoxylated alcohol remaining following incomplete alkoxylation of the mid-chain branched alcohol used to prepare the alkoxylated sulfate useful herein. It is to be recognized, however, that separate addition of such mid-chain branched alkyl sulfates is also contemplated by the present invention compositions.
  • non-sulfated mid-chain branched alcohol may comprise some amount of the alkoxylated sulfate- containing compositions.
  • Such materials may be present as the result of incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkoxylated sulfate surfactant.
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01 , preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5.
  • the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e g , ethoxylation and/or propoxylation) 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 surfactant mixtures have at least 0 001 %, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl alkoxylated sulfates having the formula
  • the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl alkoxylated sulfate having R 1 and R 2 independently hydrogen or methyl, provided R 1 and R 2 are not both hydrogen, x + y is equal to 8, 9 or 10 and z is at least 2
  • Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0 001 % to about 98 998% of a mixture of mid- chain branched primary alkyl alkoxylated sulfate surfactants, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl alkoxylated sulfates having the formula
  • M represents one or more cations
  • a, b, d, and e are integers
  • a+b is from 10 to 16
  • the surfactant composition may comprise a mixture of branched primary alkyl alkoxylated sulfates having the formula
  • R, R 1 , and R 2 are each independently selected from hydrogen and C-1-C3 alkyl, provided R, R 1 , and R 2 are not all hydrogen, M is a water soluble cation, w 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 , w + x + y + z is from 8 to 14, EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0 01,
  • R 2 is C-1-C3 alkyl comprising less than about 50%, preferably less than about 40%, more preferably less than about 25%, most preferably less than about 20%, of branched primary alkyl alkoxylated sulfate having the above formula wherein z equals 1.
  • Preferred mono-methyl branched primary alkyl ethoxylated sulfates are selected from the group consisting of: 3-methyl pentadecanol ethoxylated sulfate, 4-methyl pentadecanol ethoxylated sulfate, 5-methyl pentadecanol ethoxylated sulfate, 6-methyl pentadecanol ethoxylated sulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-methyl pentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylated sulfate, 10-methyl pentadecanol ethoxylated sulfate, 11-methyl pentadecanol ethoxylated sulfate, 12-methyl pentadecanol ethoxylated sulfate, 13-methyl pentadecan
  • Preferred di-methyl branched primary alkyl ethoxylated sulfates selected from the group consisting of: 2, 3-methyl tetradecanol ethoxylated sulfate, 2,4-methyl tetradecanol ethoxylated sulfate, 2, 5-methyl tetradecanol ethoxylated sulfate, 2,6-methyl tetradecanol ethoxylated sulfate, 2, 7-methyl tetradecanol ethoxylated sulfate, 2, 8-methyl tetradecanol ethoxylated sulfate, 2,9- methyl tetradecanol ethoxylated sulfate, 2,10-methyl tetradecanol ethoxylated sulfate, 2,11-methyl tetradecanol ethoxylated sulfate, 2, 12-methyl tetradecanol ethoxylated
  • Formylation of the alkyl halide resulting from the first hydrogenation step yields alcohol product, as shown in the scheme.
  • This can be alkoxylated using standard techniques and/or sulfated using any convenient sulfating agent, e.g., chlorosulfonic acid, S03/air, or oleum, to yield the final branched primary alkyl surfactant.
  • sulfating agent e.g., chlorosulfonic acid, S03/air, or oleum
  • Such extension can, for example, be accomplished by reaction with ethylene oxide. See “Grignard Reactions of Nonmetallic Substances", M.S. Kharasch and O. Reinmuth, Prentice-Hall, N.Y., 1954; J. Org.
  • alternate haioketones or Grignard reagents may be used.
  • PBr3 halogenation of the alcohol from formylation or ethoxylation can be used to accomplish an iterative chain extension.
  • the preferred mid-chained branched primary alkyl alkoxylated sulfates (as well as the polyoxyalkylenes and alkyl sulfates, by choosing to only alkoxylate or sulfate the intermediate alcohol produced) can also be readily prepared as follows
  • a conventional bromoalcohol is reacted with tnphenylphosphine followed by sodium hydride, suitably in dimethylsulfoxide/tetrahydrofuran, to form a Wittig adduct
  • the Wittig adduct is reacted with an alpha methyl ketone, forming an internally unsaturated methyl-branched alcoholate Hydrogenation followed by alkoxylation and/or sulfation yields the desired mid-chain branched primary alkyl surfactant
  • the Wittig approach does not allow the practitioner to extend the hydrocarbon chain, as in the Grignard sequence, the Wittig typically affords higher yields See Agricultural and Biological Chemistry, M Horiike et al , vol 42 (1978), pp 1963-1965 included herein by reference
  • the mid-chain branched primary alkyl surfacatnts may, in addition be synthesized or formulated in the presence of the conventional homologs, for example any of those which may be formed in an industrial process which produces 2-alkyl branching as a result of hydroformylation
  • Mid-chain branched surfactant mixtures are routinely added to other known commercial alkyl surfactants contained in the final laundry product formulation
  • the surfactant especially those derived from fossil fuel sources involving commercial processes, comprise at least 1 mid-chain branched primary alkyl surfactant, preferably at least 2, more preferably at least 5, most preferably at least 8
  • oxo particularly suitable for preparation of certain surfactant mixtures of the are "oxo" reactions wherein a branched chain olefin is subjected to catalytic isomenzation and hydroformylation prior to alkoxylation and/or sulfation
  • the preferred processes resulting in such mixtures utilize fossil fuels as the starting material feedstock
  • Preferred processes utilize Oxo reaction on linear olefins (alpha or internal) with a limited amount of branching
  • Suitable olefins may be made by dimerization of linear alpha or internal olefins, by controlled oligome ⁇ zation of low molecular weight linear olefins, by skeletal rearrangement of detergent range olefins, by dehydrogenation/skeletal rearrangement of detergent range paraffins, or by Fischer-Tropsch reaction
  • the suitable olefins can undergo Oxo reaction to give primary alcohols either directly or indirectly through the corresponding aldehydes
  • an Oxo catalyst is normally used which is capable of prior pre-isomerization of internal olefins primarily to alpha olefins While a separately catalyzed (i e non-Oxo) internal to alpha isome ⁇ zation could be effected, this is optional
  • the olefin-forming step itself results directly in an alpha olefin (e g with high pressure Fischer-Tropsch olefins of detergent range)
  • use of a non-isomenzing Oxo catalyst is not only possible, but preferred
  • each product comprises at total of 17 carbon atoms with linear alkyl chains having at least 13 carbon atoms
  • mid-chain branched surfactants herein where X is -C(O)- the starting material mid-chain branched carboxylic acids can be obtained from the corresponding alcohols described herein before by Jones oxidation, K Bowden, I M Heilbron, E R H Jones and B C L Weedon, J Chem, Soc 1946, 39, and H O House, Modern Synthetic Reactions (W A Benjamin, California, 2nd ed , pp 263-264) This is a chromic acid oxidation of the alcohol to the carboxylic acid in acidic media such as aqueous sulfu ⁇ c acid Acetone may be used to solubilize the alcohol and carboxylic acid The reaction is often rapid at room temperature
  • the filtrate is then cooled to 5°C at which time ethyl ether is added and let stand for 1 hour.
  • the precipitate is collected by vacuum filtration to provide the desired 7-methylheptadecyl ethoxylate (average of 1.5 ethoxylates per molecule) sulfate, sodium salt, product..
  • Chlorosulfonic acid (22.1g, 0.19 mol) is added slowly to the stirred mixture while maintaining a reaction temperature of 5-15°C with an ice water bath. After the chlorosulfonic acid is added a slow nitrogen sweep and a vacuum (10-15 inches Hg) is begun to remove HCI. Also the reaction is warmed to 30-40°C with the addition of a warm water bath. After about 45 minutes the vacuum is increased to 25-30 inches Hg and maintained for an additional 45 minutes. The acidic reaction mixture is slowly poured into a vigorously stirred beaker of 25% sodium methoxide (43.2g, 0.2 mol) and methanol (200ml) that is cooled in an ice water bath.
  • the average total carbon atoms of the branched primary alkyl surfactants herein can be calculated from the hydroxyl value of the precursor fatty alcohol mix or from the hydroxyl value of the alcohols recovered by extraction after hydrolysis of the alcohol sulfate mix according to common procedures, such as outlined in "Bailey's Industrial Oil and Fat Products", Volume 2, Fourth Edition, edited by Daniel Swern, pp. 440-441.
  • the detergent compositions comprise from about 0.001% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.1% to about 2%, by weight, of a cellulose derivative.
  • Preferred cellulose derivatives include water soluble cellulose ether derivatives, such as nonionic and cationic cellulose derivatives.
  • Anionic cellulose derivatives e.g. sodium carboxylmethyl cellulose
  • cellulose derivatives are not included within the definition of cellulose derivatives for purposes of this invention.
  • Nonionic cellulose derivatives are especially preferable.
  • the basic structure of the cellulose derivative is illustrated by the following formula:
  • n is an integer in the range of froma bout 100 to about 10,000
  • R' represents alkyl, hydroxyalkyl, or mixed alkyl and hydroxyalkyl substituents, as described hereinafter.
  • Useful alkyl groups include methyl, ethyl, propyl, buytl, pentyl, isobutyi, hexyl, nonyl, and the like.
  • Preferred alkyl groups include methyl, ethyl, propyl and butyl, with methyl being most preferred.
  • Preferred hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, with hydroxylbutyl being most preferred.
  • Highly preferred, commercially available materials have R' as mixtures of methyl and hydroxybutyl.
  • a preferred group of cellulose derivatives include methylcellulose, hydroxypropylmethylcellulose, hydroxyethyl methylcellulose, and mixtures thereof. Examples include METELOSETM, available from Shin Etsu Co.; METHOCELTM from Dow Chemical; C C 4 alkylcelluloses and C4 hydroxyalkyl celluloses.
  • a preferred cationic cellulose derivative is:
  • the detergent compositions of the invention thus may also contain additional detergent components.
  • additional detergent components and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the cleaning operation for which it is to be used.
  • Cleaning compositions herein include, but are not limited to: granular, liquid laundry detergents, and the like. Such compositions can contain a variety of conventional detersive ingredients.
  • compositions of the invention preferably contain one or more additional detergent components selected from surfactants, builders, alkalinity system, organic polymeric compounds, suds suppressors, soil suspension and anti-redeposition agents and corrosion inhibitors
  • Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein preferably further contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators Bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering If present, 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-pius-bleach activator
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes 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-nonylam ⁇ no-4-oxoperoxybutyr ⁇ c 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, Burns 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-nonylam ⁇ no-6- oxoperoxycaproic acid as described in U S Patent 4,634,551 , issued January 6, 1987 to Burns 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) can also be used
  • 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
  • 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) of the peroxy acid corresponding to the bleach activator 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 The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used See also U S 4,634,551 for other typical bleaches and activators useful herein
  • amido-de ⁇ ved bleach activators are those of the formulae R 1 N(R 5 )C(0)R 2 C(0)L or R 1 C(0)N(R 5 )R 2 C(0)L wherein R 1 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 5 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 of the nucleophilic attack on the bleach activator by the perhydroiysis anion
  • a preferred leaving group is phenyl sulfonate
  • bleach activators of the above formulae include (6-octanam ⁇ do- caproyl)oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzenesulfonate, (6-decanam ⁇ do- caproyl)oxybenzenesulfonate, and mixtures thereof as described in U S Patent 4,634,551 , incorporated 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, incorporated herein by reference
  • a highly preferred activator of the benzoxazin-type is
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-tr ⁇ methylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-tr ⁇ methylhexanoyl valerolactam and mixtures thereof See also U S Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate
  • 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 ai 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 5,114,606, and European Pat App Pub Nos 549.271A1, 549.272A1, 544.440A2, and 544.490A1 , Preferred examples of these catalysts include Mn' V 2(u-0)3(1,4,7-tr ⁇ methyl-1 ,4,7- t ⁇ azacyclononane)2(PF6)2 > Mn"'2(u-0)-
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the 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, of the catalyst species in the laundry liquor
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in M L Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv Inorq Bioinorg Mech . (1983), 2, pages 1-94
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] T y , wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]C_2, as well as [Co(NH 3 ) 5 OAc](OAc)2, [Co(NH 3 ) 5 OAc](PF 6 ) 2 , [Co(NH 3 ) 5 OAc](S0 4 ), [Co(NH 3 )5 ⁇ Ac](BF 4 )2, and [Co(NH 3 )5 ⁇ Ac](N0 3 )2 (herein "PAC”)
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0 01 ppm to about 25 ppm, more preferably from about 0 05 ppm to about 10 ppm, and most preferably from about 0 1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor
  • typical compositions herein will comprise from about 0 0005% to about 0 2%, more preferably from about 0 004% to about 0 08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions
  • Enzymes - Enzymes are preferably included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or t ⁇ glyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric launde ⁇ ng, and for fabric restoration
  • Suitable enzymes include proteases, amylases, lipases, cellulases, 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
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases
  • 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 purposes include, but are not limited to, proteases, cellulases, lipases 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
  • Enzymes are normally incorporated 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 In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0 01
  • 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
  • suitable 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
  • an especially preferred protease is a carbonyl hydrolase variant having an ammo acid sequence not found in nature, which is denved from a precursor carbonyl hydrolase by substituting a different ammo acid for a plurality of ammo acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more ammo 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 WO 95/10615 published April 20, 1995 by Genencor International
  • proteases are also described in PCT publications WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company, WO 95/30011 published Novenber 9, 1995 by The Procter & Gamble Company, WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes 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 11 , 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 These preferred 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
  • amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056
  • Specific amylase enzymes for use in the detergent compositions of the present invention include ⁇ -amylases 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 the Phadebas® ⁇ - amylase activity assay (Such Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO 95/26397 )
  • ⁇ -amylases which are at least 80% homologous with the ammo acid sequences shown in the SEQ ID listings in the references These enzymes are preferably incorporated into laundry detergent compositions at a level from 0 00018% to 0 060% pure enzyme by weight of the total composition, more preferably from 0 00024% to 0 048% pure enzyme by weight of the
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9 5 U S 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases from Humicola tnsolens or Humicola strain DSM1800 or a cellulase 212- producmg fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a manne mollusk, Dolabella Au ⁇ cula Solander Suitable cellulases are also disclosed in GB-A-2 075 028, GB-A-2 095 275 and DE-OS-2 247 832 CAREZYME® and CELLUZYME®(Novo) are especially useful See also WO 9117243 to Novo
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzen 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 Lt , 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 Corp , U S A and Disoynth Co , The Netherlands, and lipases ex Pseudomonas gladioli LIPOLASE® enzyme derived from Humicola lanugi
  • 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, iignmase, and haloperoxidases such as chloro- or bromo-peroxidase Peroxidase-containmg detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo
  • Enzyme Stabilizing System The enzyme-containing compositions herein may optionally also 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 caJcium 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 of the detergent composition
  • 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 incorporated
  • water- soluble calcium or magnesium salts are employed, including for example calcium chlo ⁇ de, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, more generally, calcium sulfate or magnesium salts corresponding 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 species See Severson, U S 4,537,706 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
  • boric acid or other borate compounds such as borax or orthoborate
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenyiboronic 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, for example automatic dishwashing 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 While chlorine
  • Suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non- structured- quid types
  • alkali metal silicates particularly those liquids and solids having a S1O2 Na2 ⁇ ratio in the range 1 6 1 to 3 2 1 , including, particularly for automatic dishwashing purposes, solid hydrous 2-rat ⁇ o silicates marketed by PQ Corp under the tradename BRITESIL®, e g , BRITESIL H20, and layered silicates, e g , those described in U S 4,664,839, May 12, 1987, H P Rieck NaSKS-6, sometimes abbreviated "SKS-6", is a
  • NaMS ⁇ x ⁇ 2 ⁇ + ⁇ yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1 9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 , as the ⁇ , ⁇ and ⁇ layer- silicate forms
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a cnspening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form XM2O yS ⁇ 2 zM'O wherein M is Na and/or K, M' is Ca and/or Mg, y/x is 0 5 to 2 0 and z/x is 0 005 to 1 0 as taught in U S 5,427,711, Sakaguchi et al, June 27, 1995
  • Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels Suitable for the present purposes are those having empirical formula [M z (Al ⁇ 2) z (S ⁇ 2) v ] XH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1 0 to 0 5, and x is an integer from 15 to 264
  • Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically derived
  • An aluminosilicate production method is in U S 3,985,669, Krummel, et al, October 12, 1976
  • Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP Natural types, including clinoptilolite, may be used
  • Detergent builders in place of or in addition to the silicates and aluminosilicates described hereinbefore can optionally be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned
  • Builder level can vary widely depending upon end use and physical form of the composition
  • Built detergents typically comprise at least about 1 % builder
  • Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder
  • Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the detergent composition
  • Lower or higher levels of builders are not excluded
  • certain detergent additive or high-surfactant formulations can be unbuilt
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts, carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate, organic mono-, d ⁇ -, tn-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types, and phytic acid
  • borates e g , for pH-buffenng purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60 1 to about 1 80
  • Certain preferred laundry detergents have said ratio in the range 0 90 1 0 to 4 0 1 0, more preferably from 0 95 1 0 to 3 0 1 0
  • P-containmg detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tnpolyphosphates, pyrophosphates, glassy polyme ⁇ c meta-phosphates, and phosphonates
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2C03 CaC ⁇ 3 when anhydrous, and even calcium carbonates including calcite, aragonite and vate ⁇ te, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars
  • Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxylates and t ⁇ carboxylates More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates
  • Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred
  • Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccmate, see Berg, U S 3,128,287, April 7, 1964, and Lamberti et al, U S 3,635,830, January 18, 1972, "TMS/TDS" builders of U S 4,663,071 , Bush et al, May 5, 1987, and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U S Patents 3,923,679, 3,835,163, 4,158,
  • Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-tr ⁇ hydroxy benzene-2, 4, 6-tr ⁇ sulphon ⁇ c acid, carboxymethyloxysuccmic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nit ⁇ lotriacetic acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene 1 ,3,5-tr ⁇ carboxyi ⁇ c acid, carboxymethyloxysuccmic acid, and soluble salts thereof
  • Citrates, e g , citric acid and soluble salts thereof are important carboxylate builders e g , for heavy duty liquid detergents, due to availability from renewable resources and biodegradability
  • Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates
  • Oxydisuccinates are also especially useful in such compositions and combinations
  • alkali metal phosphates such as sodium tnpolyphosphates, sodium pyrophosphate and sodium orthophosphate
  • Phosphonate builders such as ethane-1-hydroxy-1 ,1- diphosphonate and other known phosphonates, e g , those of U S 3,159,581 , 3,213,030, 3,422,021 , 3,400,148 and 3,422,137 can also be used and may have desirable antiscalmg properties
  • detersive surfactants or their short-chain homologs also have a builder action For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants
  • Preferred types for builder functionality are illustrated by 3,3-d ⁇ carboxy-4-oxa-1 ,6-hexaned ⁇ oates and the related compounds disclosed in U S 4,566,984, Bush, January 28, 1986
  • Succinic acid builders include the C5-C-20 alkyl and alkenyl succinic acids and salts thereof
  • Succ ate builders also include laurylsuccinate, my ⁇ stylsuccinate, palmitylsuccmate, 2-dodecenylsucc ⁇ nate (preferred), 2-pentadecenylsucc ⁇ nate, and the like Lauryl-succinates are described in European Patent Application
  • Fatty acids e g , C12-C18 monocarboxy c acids
  • surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity
  • suitable polycarboxylates are disclosed in U S 4,144 226, Crutchfield et al, March 13, 1979 and in U S 3,308,067, Diehl, March 7, 1967 See also Diehl, U S 3,723,322
  • inorganic builder materials which can be used have the formula (M x ), Ca y (C ⁇ 3) z wherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M
  • Mineral Builders Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral The charge or valence effects of such anions should be added to the right side of the above equation
  • a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium
  • the detergent compositions according to the present invention preferably further comprise additional surfactants herein also referred to as co-surfactants
  • additional surfactants herein also referred to as co-surfactants
  • the branched-chain surfactants prepared in the manner of the present invention may be used singly in cleaning compositions or in combination with other detersive surfactants
  • fully- formulated cleaning compositions will contain a mixture of surfactant types in order to obtain broad-scale cleaning performance over a variety of soils and stains and under a variety of usage conditions
  • One advantage of the branched-chain surfactants herein is their ability to be readily formulated in combination with other known surfactant types
  • additional surfactants which may be used herein typically at levels from about 1% to about 55%, by weight, include the unsaturated sulfates such as oleyl sulfate, the C-
  • the laundry detergent compositions of the present invention typically comprise from about 0 1% to about 35%, preferably from about 0 5% to about 15%, by weight of co-surfactants Selected co-surfactants are further identified as follows (1 ) Anionic Co-surfactants
  • Nonlimiting examples of anionic co-surfactants useful herein typically at levels from about 0 1% to about 50%, by weight, include the conventional C-j 1 ⁇ C-
  • alkyl alkoxy sulfate surfactants useful herein are preferably water soluble salts or acids of the formula RO(A) m S ⁇ 3M wherein R is an unsubstituted C-10-C24 alkyl or hydroxyalkyl group having a C-
  • alkyl sulfate surfactants useful herein are preferably water soluble salts or acids of the formula ROSO3M wherein R preferably is a C- ( -C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C-
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula
  • R 3 - CH(S0 3 M) - C(O) - OR 4 wherein R 3 is a C8-C2 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C1-C5 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamme, and t ⁇ ethanolamine
  • R 3 is C- j g-C ⁇ alkyl
  • R 4 is methyl, ethyl or isopropyl
  • the methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl
  • anionic co-surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and t ⁇ ethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e g , as described in British patent specification No 1,082,179, Cs- C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether
  • a preferred disulfate surfactant has the formula
  • R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C-
  • a and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length C ⁇ to C28, preferably C-j to C5, most preferably C-
  • a and B in total contain at least 2 atoms
  • A, B, and R in total contain from 4 to about 31 carbon atoms
  • X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group
  • M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal
  • the most preferred disulfate surfactant has the formula as above where R is an alkyl group of chain length from C-
  • the disulfate surfactant is typically present at levels of incorporation of from about 0 1% to about 50%, preferably from about 0 1% to about 35%, most preferably from about 0 5% to about 15% by weight of the detergent composition
  • Preferred disulfate surfactant herein include
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C 18.
  • (b) 1 ,4 disulfate compounds preferably 1 ,4 C8-C22 straight or branched chain alkyl or alkenyl disulfates, more preferably having the formula wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C13; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C-
  • These compounds may also be made by a method involving synthesis of the disulfate surfactant from a substituted cyclic anhydride having one or more carbon chain substituents having in total at least 5 carbon atoms comprising the following steps:
  • the laundry detergent compositions of the present invention typically comprise from about 0 1% to about 50%, preferably from about 1% to about 40% by weight of an anionic surfactant (2) Nonionic Co-surfactants
  • Nonlimiting examples of nonionic co-surfactants useful herein typically at levels from about 0 1% to about 50%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C-
  • condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms
  • Especially preferred nonionic surfactants of this type are the Cg-C-15 pnmary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C-12-C15 primary alcohols containing 5-10 moles of ethylene oxide per mole of alcohol
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C- ) -
  • Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula R 2 — C — N — Z ,
  • R 1 is H, or C-
  • R 2 is C5.3-1 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof
  • R 1 is methyl
  • R 2 is a straight C-
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction
  • Typical examples include the C12- 18 and C-12- 14 N-methylglucamides See U S 5,194,639 and 5,298,636 N-alkoxy polyhydroxy fatty acid amides can also be used, see U S 5,489,393
  • alkylpolysacchandes such as those disclosed in U S Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysacchande, e g a polyglycoside, hydrophilic group containing from about 1 3 to about 10, preferably from about 1 3 to about 3, most preferably from about 1 3 to about 2 7 sacchande units Any reducing sacchande containing 5 or 6 carbon atoms can be used, e g , glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc positions thus giving a glucose or galactose as opposed to a glucoside or galactoside)
  • the intersaccha ⁇ de bonds can be
  • Preferred alkylpolyglycosides have the formula
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0, and x is from about 1 3 to about 10, preferably from about 1 3 to about 3, most preferably from about 1 3 to about 2 7
  • the glycosyl is preferably derived from glucose To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position) The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-pos ⁇ t ⁇ on, preferably predominately the 2-pos ⁇ t ⁇ on Compounds of this type and their use in detergent are disclosed in EP
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000 This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF
  • compositions of the present invention may comp ⁇ se amine oxide in accordance with the general formula I
  • CH2 ' R' is preferably selected from hydrogen, methyl and -CH2OH
  • Rl IS a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R ⁇ is a primary alkyl moiety When x+y+z 0, R ⁇ is a hydrocarbyl moiety having chamlength of from about 8 to about 18 When x+y+z is different from 0, R1 may be somewhat longer, having a chamlength in the range C-12-C24
  • amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U S Patents 5,075,501 and 5,071,594, incorporated herein by reference
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R 1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms, in these embodiments y + z rs preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4, EO represents ethyleneoxy, PO represents propyleneoxy, and BO represents butyleneoxy Such amine oxides can be prepared by conventional synthetic methods, e g , by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide
  • R' is H
  • R' is CH2OH, such as hexadecylb ⁇ s(2-hydroxyethyl)am ⁇ ne oxide, tallowb ⁇ s(2-hydroxyethyl)am ⁇ ne oxide, stearylb ⁇ s(2-hydroxyethyl)am ⁇ ne oxide and oleylb ⁇ s(2- hydroxyethyl)am ⁇ ne oxide, dodecyldimethylamine oxide dihydrate (3) Cationic Co-surfactants
  • Nonlimiting examples of cationic co-surfactants useful herein typically at levels from about 0 1% to about 50%, by weight include the cholme ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like
  • Cationic co-surfactants useful as a component of the surfactant system is a cationic cholme ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i e -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
  • Preferred cationic ester surfactants are those having the formula:
  • is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M" .N + (R6R7 8)(CH2) S ;
  • X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R 2 , R3, R4, R ⁇ , R7 and R 8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C-1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the
  • R2 and R4 are independently selected from CH3 and -CH2CH2OH.
  • M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula:
  • is a C-
  • Particularly preferred choline esters of this type include the stearoyl choline ester quaternary methylammonium halides alkyl), palmitoyl choline ester quaternary methylammonium halides alkyl), myristoyl choline ester quaternary methylammonium halides -
  • alkyl), cocoyl choline ester quaternary methylammonium halides (R 1 C ⁇ -
  • the particularly preferred choline esters may be prepared by the direct este ⁇ fication of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst
  • the reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as C-
  • a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as C-
  • They may also be prepared by the direct estenfication of a long chain fatty acid of the desired chain length together with 2-
  • Suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20
  • these cationic ester surfactant are hydrolysable under the conditions of a laundry wash method
  • AQA compounds alkoxylated quaternary ammonium surfactant compounds
  • R 1 is a linear or branched alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl
  • R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 0 to about 30, preferably 1 to about 4 and q is from 0 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1. See also: EP 2,084, published May 30, 1979, by The Procter & Gamble Company, which describes cationic co-surfactants of this type which are also useful herein..
  • g enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials. Accordingly, the Ca-C- j -
  • the levels of the AQA surfactants used to prepare finished laundry detergent compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.
  • AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "E02.5", "E03.5", and the like.
  • the preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
  • R "1 is C-
  • R 1 is derived from coconut (C12-C-14 alkyl) fraction fatty acids
  • R 2 is methyl and ApR 3 and A'qR 4 are each monoethoxy, this preferred type of compound is referred to herein as "CocoMeE02" or "AQA-1" in the above list.
  • R 1 is C-jg-C-is hydrocarbyl, preferably C-
  • adjunct ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof. While the combination of the mid-chain branched primary alkyl surfactants with such adjunct compositional ingredients can be provided as finished products in the form of liquids, gels, bars, or the like using conventional techniques, the manufacture of the granular laundry detergents herein requires some special processing techniques in order to achieve optimal performance. Accordingly, the manufacture of laundry granules will be described hereinafter separately in the Granules Manufacture section (below), for the convenience of the formulator.
  • cationic co-surfactants are described, for example, in the "Surfactant Science Series, Volume 4, Cationic Surfactants” or in the "Industrial Surfactants Handbook".
  • Classes of useful cationic surfactants described in these references include amide quats (i.e., Lexquat AMG & Schercoquat CAS), giycidyl ether quats (i.e., Cyostat 609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e., Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammonium compounds (i.e., pyridinium or imidazolinium quats), and/or benzalkonium quats.
  • amide quats i.e., Lexquat AMG & Schercoquat CAS
  • giycidyl ether quats i
  • SRA Polymeric Soil Release Agent
  • SRA's can optionally be employed in the present detergent compositions. If utilized, 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, of the composition.
  • Preferred SRA's 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 SRA to be more easily cleaned in later washing procedures.
  • SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S. 4,956,447), as well as noncharged monomer units and 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.
  • Preferred 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 incorporated 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.
  • 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; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT' dimethyl terephthalate
  • PG 1,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); 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, 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
  • Suitable SRA's characterised by poly(v ⁇ nyl ester) hydrophobe segments include graft copolymers of poly(v ⁇ nyl ester), e g , C-j- Cg vinyl esters, preferably poly(v ⁇ nyl acetate), grafted onto polyalkylene oxide backbones
  • 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 90-80% by weight of polyoxyethylene terephthalate, derived from a poly
  • SRA is an oligomer having empirical formula (CAP) 2 (EG/PG)5(T)5(SIP) ⁇ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-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 Said SRA preferably further comprises from 0 5% to 20%, by weight of the oligomer, of a crystailinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenes
  • oligomeric esters comprising (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least t ⁇ functional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof, (b) at least one unit which is a terephthaloyl moiety, and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety, and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof.
  • Preferred of such esters are those of empirical formula:
  • SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyethoxy) ethoxy ⁇ ethanesulfonate (“SE3”) and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol.
  • Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ ethanesulfonate and/or sodium 2-[2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -0 3 S[CH 2 CH 2 0]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.
  • SRA's include (I) nonionic terephthalates using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al; (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 a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the 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.; (Ill) 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.
  • compositions of the 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 of the water-soluble ethoxylates amines, liquid detergent compositions typically contain about 0 01% to about 5%
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene- pentamme
  • 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 111 ,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 111 ,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 See U S Patent 4,891 ,160, VanderMeer, issued January 2, 1990
  • 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 copolyme ⁇ zing 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), fuma ⁇ c acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic 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 preferred component of the dispersmg/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 hydroxypropylacryl
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1 ,500 to about 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
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0 01% 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, couma ⁇ n, carboxylic acid, methinecyanines, d ⁇ benzoth ⁇ ophene-5,5-d ⁇ ox ⁇ de, azoles, 5- and 6-membered- ⁇ ng heterocycles, and other miscellaneous agents
  • subgroups include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, couma ⁇ n, carboxylic acid, methinecyanines, d ⁇ benzoth ⁇ ophene-5,5-d ⁇ ox ⁇ de, azoles, 5- and 6-membered- ⁇ ng heterocycles, and other miscellaneous agents
  • Examples of such brighteners are disclosed in "The Production and
  • 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 PHORWHITE series of brighteners from Verona Other brighteners disclosed in this reference include Tmopal UNPA, Tinopal CBS and Tmopal 5BM, available from Ciba-Geigy, Artie White CC and Artie White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1 ,2- djtnazoles, 4,4'-b ⁇ s-(1 ,2,3-tr ⁇ azol-2-yl)-st ⁇ lbenes, 4,4'-b ⁇ s(styryl)b ⁇ sphenyls, and the amino- coumarms Specific examples of these brighteners include 4-methyl-7-d ⁇ ethyl- am o coumarin, 1 ,2-b ⁇ s(benz ⁇ m ⁇ dazol-2-yl)ethylene, 1
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process
  • dye transfer inhibiting agents include polyvmyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrro done and N- vinylimidazole, manganese phthalocyanme, peroxidases, and mixtures thereof If used, these agents typically comprise from about 0 01% to about 10% by weight of the composition, preferably from about 0 01% to about 5%, and more preferably from about 0 05% to about 2%
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof
  • the N-0 group can be represented by the following general structures
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred 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
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolyme ⁇ zation or by an appropriate degree of N-oxidation
  • the polyamine oxides can be obtained in almost any degree of polymerization Typically, the average molecular weight is within the range of 500 to 1 ,000,000, more preferred 1 ,000 to 500,000, most preferred 5,000 to 100,000 This preferred class of materials can be referred to as "PVNO"
  • poly(4-v ⁇ nylpyr ⁇ d ⁇ ne-N-ox ⁇ de) 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-vinylpyrro done and N-vmylimidazole polymers are also preferred 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 "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference )
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrohdone from 1 1 to 0 2 1, more preferably from 0 8 1 to 0 3 1 , most preferably from 0 6 1 to 04 1
  • These copolymers can be either linear or branched
  • compositions also may employ a polyvinylpyrrolidone ("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, incorporated herein by reference
  • PVP polyvinylpyrrolidone
  • 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
  • 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 here
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula
  • R- j is selected from anilino, N-2-b ⁇ s-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-b ⁇ s-hydroxyethyl, N-2-hydroxyethyl-N-methylam ⁇ no, morphilmo, chloro and ammo
  • M is a salt-forming cation such as sodium or potassium
  • R- is anilino
  • R2 is N-2-b ⁇ s-hydroxyethyl and M is a cation such as sodium
  • the bnghtener is 4,4',-b ⁇ s[(4-an ⁇ l ⁇ no-6-(N-2-b ⁇ s-hydroxyethyl)-s-t ⁇ az ⁇ ne-2- yl)am ⁇ no]-2,2'-st ⁇ lbened ⁇ sulfon ⁇ c acid and disodium salt
  • Tmopal-UNPA-GX is commercially marketed under the tradename Tmopal-UNPA-GX by Ciba-Geigy Corporation
  • Tmopal-UNPA-GX is the preferred hydrophilic optical bnghtener useful in the detergent compositions herein
  • R- is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylam ⁇ no
  • M is a cation such as sodium
  • the bnghtener is 4,4'-b ⁇ s[(4-an ⁇ l ⁇ no-6-(N-2-hydroxyethyl-N- methylam ⁇ no)-s-tr ⁇ az ⁇ ne-2-yl)am ⁇ no]2,2'-st ⁇ lbened ⁇ sulfon ⁇ c acid disodium salt
  • Tmopal 5BM-GX by Ciba-Geigy Corporation
  • R- is anilino
  • R2 is morphilmo and M is a cation such as sodium
  • the bnghtener is 4,4'-b ⁇ s[(4-an ⁇ l ⁇ no-6-morph ⁇ l ⁇ no-s-tr ⁇ az ⁇ ne-2-yl)am ⁇ no]2,2'- stilbenedisulfonic acid, sodium salt
  • Tmopal AMS-GX is commercially marketed under the tradename Tmopal AMS-GX by Ciba Geigy Corporation
  • the specific optical bnghtener 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 polymenc materials (e g , PVNO and/or PVPVI) with such selected optical brighteners (e g , Tmopal UNPA-GX, Tmopal 5BM-GX and/or Tmopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone
  • 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 bnghtener material deposited on fabric to b) the initial bnghtener concentration in the wash liquor Brighteners with relatively high exhaustion
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelatmg agents
  • chelatmg agents can be selected from the group consisting of am o carboxylates, ammo phosphonates, polyfunctionally-substituted aromatic chelatmg 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
  • Am o carboxylates useful as optional chelatmg agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminet ⁇ acetates, nitnlotriacetates, ethylenediamine tetrapro- p ⁇ onates, triethylenetetraaminehexacetates, diethylenet ⁇ aminepentaacetates, and ethanoldi- glycmes, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein
  • Ammo phosphonates are also suitable for use as chelatmg agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST Preferred, these ammo phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms
  • Polyfunctionally-substituted aromatic chelatmg agents are also useful in the compositions herein See U S Patent 3,812,044, issued May 21 , 1974, to Connor et al Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-d ⁇ hydroxy-3,5-d ⁇ sulfobenzene
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U S Patent 4,704,233, November 3, 1987, to Hartman and Perkins
  • EDDS ethylenediamine disuccinate
  • the compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like
  • these chelatmg agents will generally comprise from about 0 1% to about 15% by weight of the detergent compositions herein More preferably, if utilized, the chelatmg agents will comprise from about 0 1% to about 3 0% by weight of such compositions
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated 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 monoearboxylic fatty acid and soluble salts therein See U S Patent 2,954,347, issued September 27, 1960 to Wayne St John
  • the monoearboxylic 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 These include, for example high molecular weight hydrocarbons such as paraffin, fatty acid esters (e g , fatty acid tnglycerides), fatty acid esters of monovalent alcohols, aliphatic C-
  • Other suds inhibitors include N-alkylated am o t ⁇ azines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlort ⁇ azines formed as products of cyanu ⁇ c 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
  • silieone suds suppressors comprises silieone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethyl- siloxane, 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.
  • Silieone 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.
  • silieone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silieone 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 silieone 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;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silieone 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 silieone uds 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 silieone resin-producing silieone 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 silieone surfactant; and (3) polyethylene glycol or a eopolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %, and without polypropylene glycol Similar amounts can be used in granular composition
  • the silieone suds suppressor herein preferably comprises polyethylene glycol and a eopolymer 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 preferred 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 eopolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300 Preferred is a weight ratio of between about 1 1 and 1 10, most preferably between 1 3 and 1 6, of polyethylene glycol eopolymer of polyethylene-polypropylene glycol
  • the preferred silieone 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 L101
  • suds suppressors useful herein comprise the secondary alcohols (e g , 2-alkyi alkanols) and mixtures of such alcohols with silieone oils, such as the silicones disclosed in U S 4,798,679, 4,075,118 and EP 150,872
  • the secondary alcohols include the CQ-C-]Q alkyl alcohols having a C-
  • a preferred 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 + silieone 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 10% of suds suppressor When utilized as suds suppressors, monoearboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silieone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the 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.
  • silieone 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, of the 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 of the finished compositions.
  • Alkoxylated Polycarboxylates Alkoxylated Polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials- are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2 ⁇ ) m (CH2) n CH 3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
  • 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 concurrently 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.
  • Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01% to about 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from about 0 0001% to about 90% of a finished perfume composition
  • Non-limiting examples of perfume ingredients useful herein include 7-acetyl-1 , 2, 3,4,5, 6,7,8-octahydro-1 , 1 ,6,7- tetramethyl naphthalene, lonone methyl, lonone gamma methyl, methyl cedrylone, methyl dihydrojasmonate, methyl 1 ,6,10-t ⁇ methyl-2,5,9-cyclododecatr ⁇ en-1-yl ketone, 7-acetyl- 1 ,1 ,3,4,4,6-hexamethyl tetra n, 4-acetyl-6-tert-butyl-1 ,1 -dimethyl indane, para-hydroxy-phenyl- butanone, benzophenone, methyl beta-naphthyl ketone, 6-acetyl-1,1 ,2,3,3,5-hexamethyl indane, 5-acet
  • perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases
  • These perfumes include but are not limited to hexyl cinnamic aldehyde, 2-methyl-3-(para-tert-butylphenyl)- propionaldehyde, 7-acetyl-1 ,2,3,4,5,6,7,8-octahydro-1,1 ,6,7-tetramethyl naphthalene, benzyl salicylate, 7-acetyl-1 ,1 ,3,4,4,6-hexamethyl tetra n, para-tert-butyl cyclohexyl acetate, methyl dihydro jasmonate, beta-napthol methyl ether, methyl beta-naphthyl ketone, 2-methyl-2-(para- ⁇ so- propylphenyl)-prop ⁇ onaldehyde, 1 ,3,4,6,7,8-hexahydro-4,6,6,
  • perfume materials include essential oils, resmoids, and resins from a variety of sources including, but not limited to Peru balsam, Olibanum resmoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin
  • perfume chemicals include phenyl ethyl alcohol, terpmeol, nalool, linalyl acetate, geraniol, nerol, 2-(1,1-d ⁇ methylethyl)- cyclohexanol acetate, benzyl acetate, and eugenol Carriers such as diethylphthalate can be used in the finished perfume compositions
  • 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, etc
  • suds boosters such as the C-
  • 4 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, betames and sultames noted above is also advantageous
  • water-soluble magnesium and/or calcium salts such as MgCl2, MgS04, CaCl2, CaS ⁇ 4 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 proteolytie enzyme solution containing 3%-5% of C- ) 3 .-
  • the enzyme/surfactant solution is 2 5 X the weight of silica
  • the resulting powder is dispersed with stirring in silieone oil (various silieone oil viscosities in the range of 500-12,500 can be used)
  • the resulting silieone oil dispersion is emulsified or otherwise added to the final detergent mat ⁇ x
  • 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 earners Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable Monohyd ⁇ c alcohols are preferred for solubiliz g 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-propaned ⁇ ol, ethylene glycol, glycerine, and 1 ,2-propaned ⁇ ol) 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, du ⁇ ng use in aqueous cleaning operations, the wash water will have a pH of between about 6 5 and about 11, 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 9-11. 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. Form of the compositions
  • compositions in accordance with the invention can take a variety of physical forms including granular, tablet, and liquid forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre.
  • Replicate measurements are made as required.
  • the mid-chain branched primary alkyl surfactant system herein is preferably present in granular compositions in the form of mid-chain branched primary alkyl surfactant agglomerate particles which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules
  • the most preferred way to process the particles is by agglomerating powders (e g aluminosilicate, carbonate) with high active mid-chain branched primary alkyl surfactant pastes and to control the particle size of the resultant agglomerates within specified limits
  • agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder
  • a high active mid-chain branched primary alkyl surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of mid-chain branched primary alkyl surfactant is typically used
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the surfactants used
  • An operating temperature of the paste of 50°C to 80°C is typical Laundry washing method
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention
  • an effective amount of the detergent composition it is meant from 20g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods
  • mid-chain branched primary alkyl surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels which are effective for achieving at least a directional improvement in cleaning performance
  • usage levels can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine
  • a wash cycle of about 10 to about 14 minutes and a wash water temperature of about 10°C to about 50°C it is preferred to include from about 2 ppm to about 625 ppm, preferably from about 2 ppm to about 550 ppm, more preferably from about 10 ppm to about 235 ppm, of the mid-chain branched primary alkyl surfactant in the wash liquor
  • this translates into an m-product concentration (wt ) of the mid-chain branched primary alkyl surfactant of from about 0 1% to about 40%, preferably about 0 1% to about 35%, more preferably from about 0 5% to about 15%, for a heavy-duty liquid laundry detergent
  • wt m-product concentration
  • a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30°C to about 95°C it is preferred to include from about 3 ppm to about 14,000 ppm, preferably from about 3 ppm to about 10,000 ppm, more preferably from about 15 ppm to about 4200 ppm, of the mid-chain branched primary alkyl surfactant in the wash liquor
  • this translates into an m-product concentration (wt ) of the mid-chain branched primary alkyl surfactant of from about 0 1% to about 50%, preferably about 0 1% to about 35%, more preferably from about 0 5% to about 15%, for a heavy-duty liquid laundry detergent
  • wt m-product concentration
  • a wash cycle of about 8 to about 15 minutes and a wash water temperature of about 5°C to about 25°C it is preferred to include from about 0 67 ppm to about 270 ppm, preferably from about 067 ppm to about 236 ppm, more preferably from about 3 4 ppm to about 100 ppm, of the mid-chain branched primary alkyl surfactant in the wash liquor
  • this translates into an m-product concentration (wt ) of the mid-chain branched primary alkyl surfactant of from about 0 1% to about 40%, preferably about 0 1% to about 35%, more preferably from about 0.5% to about 15%, for a heavy-duty liquid laundry detergent.
  • the amount of mid-chain branched primary alkyl surfactant used in a machine-wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine, and the like.
  • one heretofore unappreciated advantage of the mid-chain branched primary alkyl surfactants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains even when used at relatively low levels with respect to the other surfactants (generally anionics or anionic/nonionic mixtures) in the finished compositions.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the dispensing device containing the detergent product is placed inside the drum.
  • water is introduced into the drum and the drum periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents, GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A- 0288346
  • An article by J Bland published in Manufacturing Chemist, November 1989, pages 41- 46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette”
  • Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No W094/11562
  • European Patent Application Publication Nos 0343069 & 0343070 discloses a device comp ⁇ sing a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium
  • the support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form
  • the dispensing device may be a flexible container, such as a bag or pouch
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No 0018678
  • it may be formed of a water-insoluble synthetic polymeric matenal provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos 0011500, 0011501 , 0011502, and 0011968
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • TPK Fatty Acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
  • Bnghtener 3 Disodium 4,4'-b ⁇ s((4-an ⁇ l ⁇ no-6-b ⁇ s(2-hydroxyethyl) am ⁇ no-1 ,3,5-t ⁇ az ⁇ n-2-y)am ⁇ no) st ⁇ bene-2,2' - disulfonate
  • Bnghtner 4 Disodium 4,4'-b ⁇ s((4-an ⁇ l ⁇ no-6-(N-methyl-N-2- hydroxyethyl)am ⁇ no-1 ,3,5-t ⁇ az ⁇ n-2-yl)am ⁇ no)st ⁇ lbene-
  • laundry detergent compositions A to D are prepared in accord with the invention:
  • laundry detergent compositions J to O are prepared in accord with the invention:
  • laundry detergent compositions O to R are prepared in accord with the invention:
  • liquid laundry detergent compositions AA to DD are prepared in accord with the invention:
  • liquid laundry detergent compositions EE to II are prepared in accord with the invention:
  • MBAS (14.5-15.5 ave. 6.25 10.5 14.75 19 total carbon)
  • laundry detergent compositions A to D are prepared in accord with the invention:
  • laundry detergent compositions J to O are prepared in accord with the invention:
  • laundry detergent compositions 0 to R are prepared in accord with the invention:
  • liquid laundry detergent compositions AA to DD are prepared in accord with the invention:
  • laundry detergent compositions A to I are prepared in accord with the invention:
  • laundry detergent compositions J to N are prepared in accord with the invention:
  • laundry detergent compositions O to S are prepared in accord with the invention:
  • liquid laundry detergent compositions W to Z are prepared in accord with the invention:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions détergentes, par exemple celles permettant de laver des tissus, la vaisselle ou des surfaces dures. Ces compositions renferment au moins environ 0,5 % d'une chaîne alkyle plus longue, de composés tensioactifs ramifiés en milieu de chaîne et entre environ 0,001 % et environ 10 %, en poids, d'un dérivé cellulosique.
PCT/US1997/018841 1997-10-10 1997-10-10 Tensioactifs ramifies en milieu de chaine avec derives cellulosiques WO1999019445A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP50062599A JP3308548B2 (ja) 1997-10-10 1997-10-10 セルロース誘導体を含む中鎖分岐界面活性剤
US09/529,261 US6242406B1 (en) 1997-10-10 1997-10-10 Mid-chain branched surfactants with cellulose derivatives
AU50821/98A AU5082198A (en) 1997-10-10 1997-10-10 Mid-chain branched surfactants with cellulose derivatives
CA002305330A CA2305330A1 (fr) 1997-10-10 1997-10-10 Tensioactifs ramifies en milieu de chaine avec derives cellulosiques
PCT/US1997/018841 WO1999019445A1 (fr) 1997-10-10 1997-10-10 Tensioactifs ramifies en milieu de chaine avec derives cellulosiques
BR9714877-6A BR9714877A (pt) 1997-10-10 1997-10-10 "tensoati-vos de cadeia ramificada no meio com derivados celulose"
EP97913694A EP1021510A1 (fr) 1997-10-10 1997-10-10 Tensioactifs ramifies en milieu de chaine avec derives cellulosiques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/018841 WO1999019445A1 (fr) 1997-10-10 1997-10-10 Tensioactifs ramifies en milieu de chaine avec derives cellulosiques

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WO1999019445A1 true WO1999019445A1 (fr) 1999-04-22

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544296B2 (en) * 2000-02-07 2003-04-08 The Proctor & Gamble Company Enhanced fabric comprising substrates and process to provide same
WO2006113313A1 (fr) * 2005-04-15 2006-10-26 The Procter & Gamble Company Detergent pour lessive contenant des tensio-actifs de sulfate d'alkyle primaire ramifie a mi-chaine
DE102011000889A1 (de) * 2011-02-23 2012-08-23 Witty Chemie Gmbh & Co. Kg Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
EP2512531A1 (fr) * 2009-12-17 2012-10-24 The Procter & Gamble Company Composition détergente permettant de laver la vaisselle et renfermant un composant de neutralisation des mauvaises odeurs et procédés de nettoyage de vaisselle
WO2014012869A1 (fr) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Détergent liquide stable à capacité antiredéposition
JP2016520148A (ja) * 2013-05-24 2016-07-11 ザ プロクター アンド ギャンブル カンパニー コンパクト流体洗濯洗剤組成物
EP3101102A1 (fr) * 2015-06-05 2016-12-07 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
US20160355766A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
US20160355767A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
US20160355754A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition

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JP4534193B2 (ja) * 2004-02-02 2010-09-01 花王株式会社 粉末洗剤組成物
JP5378140B2 (ja) * 2009-10-07 2013-12-25 花王株式会社 液体洗浄剤組成物の製造方法
JP6052777B2 (ja) * 2012-12-26 2016-12-27 花王株式会社 液体洗浄剤組成物
JP6472984B2 (ja) * 2014-11-12 2019-02-20 花王株式会社 手洗い用食器洗浄剤組成物
JP2018104704A (ja) * 2016-12-27 2018-07-05 花王株式会社 繊維製品用粉末洗浄剤組成物

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EP0130609A2 (fr) * 1983-07-05 1985-01-09 Kao Corporation Suspension liquide à apparence perlée
WO1997039091A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Tensioactifs ramifies en milieu de chaine

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JPS57133200A (en) * 1981-02-10 1982-08-17 Kao Corp Detergent composition
EP0130609A2 (fr) * 1983-07-05 1985-01-09 Kao Corporation Suspension liquide à apparence perlée
WO1997039091A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Tensioactifs ramifies en milieu de chaine

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DATABASE WPI Section Ch Week 8238, Derwent World Patents Index; Class A97, AN 82-80582E, XP002066464 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6544296B2 (en) * 2000-02-07 2003-04-08 The Proctor & Gamble Company Enhanced fabric comprising substrates and process to provide same
WO2006113313A1 (fr) * 2005-04-15 2006-10-26 The Procter & Gamble Company Detergent pour lessive contenant des tensio-actifs de sulfate d'alkyle primaire ramifie a mi-chaine
EP2512531A1 (fr) * 2009-12-17 2012-10-24 The Procter & Gamble Company Composition détergente permettant de laver la vaisselle et renfermant un composant de neutralisation des mauvaises odeurs et procédés de nettoyage de vaisselle
DE102011000889A1 (de) * 2011-02-23 2012-08-23 Witty Chemie Gmbh & Co. Kg Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
WO2014012869A1 (fr) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Détergent liquide stable à capacité antiredéposition
JP2016520148A (ja) * 2013-05-24 2016-07-11 ザ プロクター アンド ギャンブル カンパニー コンパクト流体洗濯洗剤組成物
WO2016196704A1 (fr) * 2015-06-05 2016-12-08 The Procter & Gamble Company Composition de détergent à lessive liquide compactée
US20160355766A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
EP3101102A1 (fr) * 2015-06-05 2016-12-07 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
US20160355767A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
US20160355763A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
US20160355754A1 (en) * 2015-06-05 2016-12-08 The Procter & Gamble Company Compacted liquid laundry detergent composition
CN107690473A (zh) * 2015-06-05 2018-02-13 宝洁公司 致密液体衣物洗涤剂组合物
RU2679797C1 (ru) * 2015-06-05 2019-02-13 Дзе Проктер Энд Гэмбл Компани Уплотненная композиция жидкого моющего средства для стирки
US10655093B2 (en) * 2015-06-05 2020-05-19 The Procter & Gamble Company Compacted liquid laundry detergent composition
US10711225B2 (en) * 2015-06-05 2020-07-14 The Procter & Gamble Company Compacted liquid laundry detergent composition

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AU5082198A (en) 1999-05-03
EP1021510A1 (fr) 2000-07-26
JP3308548B2 (ja) 2002-07-29
JP2000513045A (ja) 2000-10-03
CA2305330A1 (fr) 1999-04-22

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