EP1023421A1 - A detergent composition - Google Patents

A detergent composition

Info

Publication number
EP1023421A1
EP1023421A1 EP97913672A EP97913672A EP1023421A1 EP 1023421 A1 EP1023421 A1 EP 1023421A1 EP 97913672 A EP97913672 A EP 97913672A EP 97913672 A EP97913672 A EP 97913672A EP 1023421 A1 EP1023421 A1 EP 1023421A1
Authority
EP
European Patent Office
Prior art keywords
integer
surfactant
alkyl
preferred
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP97913672A
Other languages
German (de)
French (fr)
Inventor
Frank Andrej Kvietok
Gabor Heltovics
Francisco Ramon Figueroa
Kenneth William Willman
Michael Alan John Moss
Rinko Kobe Park City C507 KATSUDA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1023421A1 publication Critical patent/EP1023421A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention relates to detergent compositions comprising anionic mid- branched surfactant compounds and additional anionic sulfate and sulfonate surfactants.
  • the compositions are particularly useful as solid laundry detergent compositions.
  • mid-chain branched surfactants are excellent surfactants, in particular for use in laundry products, especially under cool or cold water washing conditions even as low as 20°C-5°C. It has also been found that combination of two or more of these mid-chain branched surfactants can provide a surfactant mixture that is even higher in surfactancy and has better low temperature water solubility.
  • detergent compositions comprising these mid-chain branched surfactants and an additional sulphate and sulphonate surfactant, present in specific ratios, has an improved cleaning performance, in particular of greasy stains and soils. It has been found that lower levels of the additional anionic sulfate and sulfonate surfactants, which are traditionally known and used in detergent formulations, can still have excellent cleaning performance when combined with the mid-chain branched anionic surfactants.
  • An additional benefit of such a combination can be that it allows the reduction of the levels of (or even the elimination of) other surfactants which are traditionally employed in detergents, such as nonionic surfactants, whilst still achieving an excellent cleaning performance.
  • the inclusion of the specific mid-chain branched surfactants in detergent compositions comprising anionic sulfate and sulfonate surfactants allows an overall reduction of the levels and types of surfactants needed, to obtain excellent cleaning performance.
  • Another additional benefit is that hereby the formulation costs can be reduced and the ease of formulation can be improved.
  • the invention relates to detergent compositions, preferably being solid laundry detergent compositions, comprising
  • composition a surfactant system, comprising one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula:
  • a D is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, 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 ⁇ - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the - X
  • the average total number of carbon atoms in the A D -X moieties in the above formula is within the range of greater than 14.5 to about 18, preferably from about 15 to about 17;
  • (II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polygly
  • X is selected from -CH2- and -C(O)-;
  • ratio of the surfactant system a) to the surfactant b) is from 20:1 to 1 :20 and the ratio of surfactant system a) to the surfactant c) is from 20:1 to 1 :10.
  • the surfactant system a) comprises mid-chain branched primary alkyl sulfate or sulfonate surfactants.
  • the detergent compositions of the invention comprise at least 0.5%>, preferably at least 5%, more preferably at least 10% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds, selected from the group consisting of surfactant compounds having the formula as defined above.
  • Preferred surfactant systems 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% and R2 are each independently selected from hydrogen and C ⁇ -C3 alkyl (preferably methyl), provided R, Rl, and R ⁇ are not all hydrogen and, when z is 0, at least R or Rl 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.
  • mid-chain branched surfactant compounds of the surfactant system certain points of branching (e.g., the location along the chain of the R, R*, 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 D moieties useful according to the present invention.
  • surfactant compounds wherein in the above formula the A D moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).
  • the most preferred mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants.
  • Preferred mid-chain branched primary alkyl_sulfate surfactants are of the formula
  • These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms.
  • the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5.
  • the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not 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 moiety is within the range of greater than 14.5 to about 17.5.
  • R, Rl, and R ⁇ are each independently selected from hydrogen and Ci -C3 alkyl group (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R , and R ⁇ are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.
  • 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
  • Preferred cations are ammonium (R- ⁇ , R4, R5 and R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
  • the monoalkanol ammonium compounds of the present invention have R3 equal to C1 -C6 alkanol, R , R5 and R ⁇ equal to hydrogen; dialkanol ammonium compounds of the present invention have R ⁇ and R4 equal to C]-C6 alkanol, R-* and R" equal to hydrogen; trialkanol ammonium compounds of the present invention have R- ⁇ , R4 and R ⁇ equal to Ci -Cg alkanol, R ⁇ equal to hydrogen.
  • Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
  • Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium.
  • Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula
  • the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight , even more preferably at least 90% by weight of the system, of mid-chain branched primary alkyl sulfates, preferably having Rl and R ⁇ independently hydrogen or methyl, provided Rl and R ⁇ are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 14 to 18, more preferably from 15 to 17, even more preferably from 16 to 17.
  • preferred surfactant systems are those, which comprise at least about 20%, more preferably at least 60%, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula:
  • 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 pent
  • branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
  • M is preferably sodium
  • branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
  • M is preferably sodium
  • the detergent compositions of the present invention comprise an additional sulfonate surfactant.
  • This surfactant can be any sulfonate surfactant known in the art, not being a sufonate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfonate surfactants are described herein.
  • the ratio of the surfactant system to the additional sulfonate surfactant is preferably from 10:1 to 1 :5, more preferably from 5:1 to 1 :1, even more preferably
  • Preferred additional sulfonate surfactants for the detergent compositions of the present invention are the salts of C5-C20 linear alkylbenzene sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof. Highly preferred is a Cl 1-C16 linear alkylbenzene sulphonate.
  • Preferred salts are sodium and potassium salts.
  • Alkyl ester sulphonated surfactant are other preferred additional sulfonate surfactants for the detergent compositions of the invention. Preferred are those of the formula
  • Rl is a C6-C22 hydrocarbyl
  • R 2 is a C ⁇ -Cg alkyl
  • A is a Cg-C22 alkylene
  • alkenylene x is 0 or 1
  • M is a cation.
  • Preferred is an -methyl ester sulfonate surfactant.
  • the counterion M is preferably sodium, potassium or ammonium.
  • the alkyl ester sulphonated surfactant is preferably a -sulpho alkyl ester of the formula above, whereby thus x is 0.
  • R is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0.
  • R is preferably ethyl or more preferably methyl.
  • Rl of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.
  • the detergent compositions of the present invention comprise an additional sulfate surfactant.
  • This surfactant can be any sulfate surfactant known in the art, not being a sufate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfate surfactants are described herein.
  • the ratio of the surfactant system to the additional sulfate surfactant is preferably from 10:1 to 1 :10, more preferably from 4:1 to 1 :2, even more preferably from 2:1 to 1 :2.
  • Anionic (mono) sulfate surfactants are preferred additional sulfate surfactants for use in the detergent compositions of the present invention.
  • These include the linear and branched, other than mid-chain branched surfactants of the invention, primary and secondary saturated and unsaturated alkyl sulfates, alkyl ethoxysulfates having an average ethoxylation number of from 0.5 to 15, preferably from 3 to 7, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj- C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides. or glucosides
  • Primary alkyl mono-sulfate surfactants are preferably selected from the linear and branched primary CjQ-Cig alkyl sulfates, more preferably the C12-C15 chain alkyl sulfates and the C12-C15 linear chain alkyl sulfates.
  • Preferred secondary alkyl mono-sulfate surfactant are of the formula
  • R is a C 8 -C 20 hydrocycarbyl
  • R is a hydrocycarbyl
  • M is a cation
  • Alkyl ethoxy mono-sulfate surfactants are preferably selected from the group consisting of the CI Q-CI g alkyl sulphates which have been ethoxylated with from 0.5 to 15 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a 5 alkyl sulfate which has been ethoxylated with from 3 to 9, preferably from 3 to 7, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants.
  • Preferred salts are sodium and potassium salts.
  • the additional sulfate surfactant or the additional sulfonate surfactant of the detergent compositions of the invention can also comprise dianionic surfactants, which comprise two anionic groups, each of which can be independently a sulfate or sufonate group, but which can also be a sulfate and a sulfonate group.
  • these dianionc surfactants are to be considered either additional sulfate or additional sulfonate surfactants for use in the detegergent compositions of the inevntion, depending on their anionic groups.
  • dianionic surfactants for use in the detergent compositions of the present invention are of the formula:
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C2g, preferably C3 to C24, most preferably Cg to C20 > or hydrogen;
  • a nad B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C] to C2g preferably C1 to C5, most preferably C ⁇ or C2, or a covalent bond, and preferably 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 comprising carboxylate, and preferably sulfate and sulfonate, provided that al least one anionic group X or y is a sulfate or a sulfonate group, z
  • the most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from CJ Q to Cjg, A and B are independently Cj or C2, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • Preferred dianionic surfactants herein include:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C 20;
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C1 g; 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 C1 g.
  • dianionic surfactants of the invention are alkoxylated dianionic surfactants.
  • the alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy-linked sulphate or sulphonate group.
  • Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.
  • Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof
  • the structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms.
  • the structural skeleton comprises only carbon- containing groups and more preferably comprises only hydrocarbyl groups.
  • the structural skeleton comprises only straight or branched chain alkyl groups.
  • the structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching).
  • a preferred alkoxylated dianionic surfactant has the formula
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C2 , preferably C3 to C24, most preferably Cg to C20 > or hydrogen;
  • a and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length C1 to C2 , preferably Cj to C5, most preferably C1 or C2, or a covalent bond;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1 ;
  • 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 sulphate and sul
  • the most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from C1 Q to C1 g, A and B are independently C1 or C2, n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • the alkoxylated dianionic cleaning agent is typically present at levels of incorporation of from about 0.1 % to about 20%, preferably from about 0.3% to about 15%), most preferably from about 0.5% to about 10% by weight of the bleaching detergent composition.
  • Preferred alkoxylated dianionic surfactants herein include: ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about Ci g;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and
  • n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.
  • the detergent compositions in accord with the invention may also contain additional detergent components.
  • additional detergent components and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
  • compositions of the invention preferably contain one or more additional detergent components selected from other surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • additional detergent components selected from other surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • the detergent compositions in accord with the invention can contain one or more other surfactants selected from nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • nonionic, ampholytic, and zwitterionic classes, and species of these surfactants is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
  • the nonionic surfactants are preferably present in low levels, preferably from 0.5% to 20%, more preferably from 1% to 15%, even more preferably from 1.5% to 8% by weight.
  • the ratio of the nonionic surfactants, when present, to the surfactant system is preferably from 5:1 to 1 :20, more preferably from 5:1 to 1 :10, even more preferably from 1 :1 to 1 :10.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propyiene glycol, and the nonionic ethoxylate condensation products with propyiene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propyiene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms or more preferably 9 to 15 with from 3 to 12 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C ⁇ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z
  • Suitable fatty acid amide surfactants include those having the formula: R6cON(R )2 wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, Ci -C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from l to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR4) ⁇ N ⁇ (R )2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R-> is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Ci o-Cj alkyl dimethylamine oxide, and Cjo-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R 2 COO ⁇ wherein R is a C -C1 g hydrocarbyl group, each R is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the CJ O-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants to be used in the detergent include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono Cg-Ci 5, preferably C6-C1 Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising 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 US Patents No.s 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e.
  • spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • the cationic mono-alkoxylated amine surfactant are preferably of the general formula I:
  • Rl is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
  • R 2 and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R ⁇ are methyl groups;
  • R is selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
  • p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A is ethoxy and R4 is hydrogen and p is 1, R1 is not a C12-C14 alkyl group.
  • Particularly preferred ApR 4 groups are — CH2CH2OH, — CH2CH2CH2OH, — CH 2 CH(CH 3 )OH and— CH(CH 3 )CH 2 OH, with — CH 2 CH 2 OH being particularly preferred.
  • Preferred R groups have have no greater than 10 carbon atoms, or even no greater than 8 or 9 carbon atoms.
  • Preferred Rl groups are linear alkyl groups.
  • Linear Rl groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
  • Such a cationic surfactant which is highly preferred has a formula wherein R1 is a Cg-Cjo alkyl group, p is 1, A is ethoxy and R2 and R3 are methyl groups.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • R is CJ O-CI g hydrocarbyl and mixtures thereof, especially C10- 14 alkyl, preferably CJQ and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2 ⁇ ] and [CH2CH(CH3 ⁇ ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and or i-Pr units.
  • EO ethoxy
  • i-Pr isopropoxy
  • Pr n-propoxy units
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%), more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.
  • the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
  • Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R4 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 mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • Rl is C ⁇ Q-Ci hydrocarbyl and mixtures thereof, preferably CI Q, 12, C14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • Rl is Cjo-Cjg hydrocarbyl, preferably Ci 0-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • the levels of the cationic bis-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4%) to 7%, most preferably from 0.5% to 3.0% by weight of the composition.
  • Suitable optional soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l- heptanoic acid. Certain soaps may also be included as suds suppressors.
  • anionic surfactants are the carboxylate-based anionic surfactants known in the art and alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1 -C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C1 -C4 alkyl group
  • M is an alkali metal ion.
  • the detergent compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • the detergent compositions of the invention can comprise phosphate-containing builder material, preferably present at a level of from 0.015 to 50%, more preferably from 5% to 30%, more preferably from 8% to 25%, most preferably from 12% to 205 by weight of the composition.
  • the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate. . It can be preferred that the compositions are free form phosphate-containing builders
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fiimaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present a t a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1, 2,3 -propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • the detergent compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • Zeolite X has the formula Nagg [(AlO 2 )g6(SiO2)i06]- 2 76 H 2 O.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40%) by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A. Perhydrate Bleaches
  • An preferred additional components of the detergent composition is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • a preferred feature of detergent composition is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%) to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
  • Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15%> by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP- A-0170386.
  • Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • the bleach system can contain a transition metal containing bleach catalyst.
  • One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnI ⁇ 2( u -C)3(l 5 4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2 5 MnH ⁇ u- O) i (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(ClO4)2, Mnl V 4(u- O)6(l,4,7-triazacyclononane) 4 -(ClO4)2, Mn ⁇ MnI V 4(u-O) ⁇ (u-OAc)2_(l,4,7- trimethyl-l,4,7-triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof.
  • ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-triazacyclononane, and mixtures thereof.
  • bleach catalysts useful herein may also be selected as appropriate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- 1,4,7- triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, marmitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Said ligands are of the formula:
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and - bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'- bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4, Bis- (2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands including N4MnIH(u-O)2Mn VN4) + and [Bipy2MnIH(u-
  • bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
  • the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
  • catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted.
  • 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 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
  • 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.
  • Another preferred ingredient useful in the detergent is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally inco ⁇ orated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be inco ⁇ orated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be inco ⁇ orated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%) to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001%) to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti- redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quaternised ethoxylated (poly) amine clay- soil removal/ anti-redeposition agent in accord with the invention.
  • Organic polymeric compound is typically inco ⁇ orated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Te ⁇ olymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for inco ⁇ oration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci g-C4Q ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propyiene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a preferred suds suppressing system comprises:
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound
  • silica/silicone antifoam compound is inco ⁇ orated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propyiene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C 1 g-C ⁇ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures : O
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N- oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Co ⁇ oration, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Co ⁇ oration.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxy ethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R1 is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • R1 is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • SRA polymeric soil release agents
  • 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 compositions.
  • 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 the SRA to be more easily cleaned in later washing procedures.
  • 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 inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxy lating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • SRA's include the nonionic end-capped 1 ,2-propylene/polyoxy ethylene terephthalate polyesters of U.S.
  • Gosselink et al. for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5- sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propyiene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1 -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals 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..
  • Other classes include: (III) anionic terephthalate- based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other Optional Ingredients
  • compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions preferably contain from about 2% to about 10% by weight of an organic citric acid, preferably citric acid. Also preferably in combination with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein inco ⁇ orated by reference), can be present in the compositions.
  • neutralizing agents e.g., less than about 20% by weight
  • buffering agents e.g., phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in US Patent 4,285,841 to Barrat et al
  • compositions in accordance with the invention can take a variety of physical forms including liquid but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
  • compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach, as mentioned above.
  • preferred detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.
  • the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
  • the chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution.
  • the hypochlorite ion is chemically represented by the formula OCT.
  • Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hyposchlorite addition products, chloramines, chlorimines, chloramides, and chlorimides.
  • compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B.
  • a preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof.
  • a preferred chlorine- based bleach can be Triclosan (trade name).
  • hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
  • granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
  • the mid-chain branched surfactant system herein preferably with the additional sulfate and/ or sulfonate surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, preferably not comprising the bleach precursors, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • the most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
  • Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1 , Elsener
  • a high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of the surfactants, including the mid- chain branched surfactants, is typically used.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 25%> of the particles are greater than 1.8mm in diameter and not more than 25% of the particles are less than 0.25mm in diameter.
  • the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm 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 sieves, preferably 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 200 g/litre, more preferably from 300 g/litre to 1400 g/litre, more preferably from 330g/litre to 1200 gr/litre, most preferably from 380 g/litre to 850 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.
  • 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 lOg 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.
  • the detergent composition is formulated such that it is suitable for hand washing.
  • the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
  • TAS Sodium tallow alkyl sulfate
  • CxyEzS Sodium C ⁇ x -Ci y branched alkyl sulfate condensed with z moles of ethylene oxide MBAS X> y : Sodium mid-chain branched alkyl sulfate having an average of x carbon atoms, whereof an average of y carbons comprised in (a) branching unit(s)
  • Nai2(A102SiO2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • NAC-OBS Nonanamido caproyl oxybenzene sulfonate in the form of the sodium salt.
  • NACA 6 nonylamino - 6 oxo - capronic acid NACA 6 nonylamino - 6 oxo - capronic acid.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino- 1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
  • compositions G to I of bulk density 750 g/litre are compositions according to the invention:
  • J is a phosphorus-containing detergent composition
  • K is a zeolite-containing detergent composition
  • L is a compact detergent composition
  • laundry detergent compositions AQ to AT are prepared in accord with the invention:
  • laundry detergent compositions AU to AY are prepared in accord with the invention:
  • laundry detergent compositions AZ to Ee are prepared in accord with the invention:

Abstract

The present invention relates to detergent compositions comprising anionic mid-branched surfactant compounds and additional anionic sulfate and sulfonate surfactants. The compositions are particularly useful as solid laundry detergent compositions.

Description

A Detergent Composition
Technical Field
The present invention relates to detergent compositions comprising anionic mid- branched surfactant compounds and additional anionic sulfate and sulfonate surfactants. The compositions are particularly useful as solid laundry detergent compositions.
Background to the Invention
Recently, a certain new type of anionic mid-chain branched surfactants has been developed. These surfactants are described in unpublished co-pending applications US 97/06485, US 97/06474, US 97/06339, US 97/06476 and US 97/06338.
It has been determined that these mid-chain branched surfactants are excellent surfactants, in particular for use in laundry products, especially under cool or cold water washing conditions even as low as 20°C-5°C. It has also been found that combination of two or more of these mid-chain branched surfactants can provide a surfactant mixture that is even higher in surfactancy and has better low temperature water solubility.
Surprisingly, it has now been found that detergent compositions comprising these mid-chain branched surfactants and an additional sulphate and sulphonate surfactant, present in specific ratios, has an improved cleaning performance, in particular of greasy stains and soils. It has been found that lower levels of the additional anionic sulfate and sulfonate surfactants, which are traditionally known and used in detergent formulations, can still have excellent cleaning performance when combined with the mid-chain branched anionic surfactants. An additional benefit of such a combination can be that it allows the reduction of the levels of (or even the elimination of) other surfactants which are traditionally employed in detergents, such as nonionic surfactants, whilst still achieving an excellent cleaning performance. Thus, the inclusion of the specific mid-chain branched surfactants in detergent compositions comprising anionic sulfate and sulfonate surfactants, allows an overall reduction of the levels and types of surfactants needed, to obtain excellent cleaning performance. Another additional benefit is that hereby the formulation costs can be reduced and the ease of formulation can be improved.
All documents cited are hereby incorporate herein by reference.
Summary of the Invention
The invention relates to detergent compositions, preferably being solid laundry detergent compositions, comprising
a) at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition a surfactant system, comprising one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula:
A - X - B
wherein:
(I) AD is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, 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\ - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the - X
- B moiety, to the position of the terminal carbon minus 2 carbons, (the (ω - 2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the AD-X moieties in the above formula is within the range of greater than 14.5 to about 18, preferably from about 15 to about 17;
(II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quats, alkyated/polyhydroxyalkylated quats, alkylated quats, alkylated/polyhydroxylated oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and
(III) X is selected from -CH2- and -C(O)-; and
b) at least about 0.5%, preferably at least about 5%, more preferably at least about 10%) by weight of the composition of an additional sulfate surfactant; and
c) at least about 0.5%, preferably at least about 5%, more preferably at least about 10% by weight of the composition of an additional sulfonate surfactant,
whereby the ratio of the surfactant system a) to the surfactant b) is from 20:1 to 1 :20 and the ratio of surfactant system a) to the surfactant c) is from 20:1 to 1 :10.
Preferably, the surfactant system a) comprises mid-chain branched primary alkyl sulfate or sulfonate surfactants.
Detailed Description of the Invention
Mid-Chain Branched Surfactant Compounds-Containing Surfactant System
The detergent compositions of the invention comprise at least 0.5%>, preferably at least 5%, more preferably at least 10% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds, selected from the group consisting of surfactant compounds having the formula as defined above.
Preferred surfactant systems herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the AD moiety is a branched primary alkyl moiety having the formula:
R Rl R2
I I I
CH3CH2(CH2)wCH(CH2)xCH(CH2)yCH(CH2)z- wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, Rl, and R^ branching) is from 13 to 19; R, R% and R2 are each independently selected from hydrogen and C \ -C3 alkyl (preferably methyl), provided R, Rl, and R^ are not all hydrogen and, when z is 0, at least R or Rl 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.
In general, for the mid-chain branched surfactant compounds of the surfactant system, certain points of branching (e.g., the location along the chain of the R, R*, 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 AD moieties useful according to the present invention.
CH3CH2CH2CH2CH2CH2(CH2) 1.7CH2CH2CH2CH2CH2-
mid-chain branching range-
It should be noted that for the mono-methyl substituted surfactants these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X - B group.
The formula below illustrates the mid-chain branching range, preferred mid-chain branching range, and more preferred mid-chain branching range for di-methyl substituted alkyl AD moieties useful according to the present invention.
CH3CH2CH2CH2CH2CH2(CH2)o-6CH2CH2CH2CH2CH2 -
more preferred range — preferred range — mid-chain branching range
Preferred are surfactant compounds wherein in the above formula the AD moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom). The most preferred mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants.
Preferred mid-chain branched primary alkyl_sulfate surfactants are of the formula
These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not 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 moiety is within the range of greater than 14.5 to about 17.5.
R, Rl, and R^ are each independently selected from hydrogen and Ci -C3 alkyl group (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R , and R^ are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.
M is hydrogen or a salt forming cation depending upon the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula
R3
R6— N l -+ R4 Λ wherein R^, R4, R5 and R6 ^Q independently hydrogen, C\ -C22 alkylene, C4-C22 branched alkylene, CJ-C6 alkanol, C1 -C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof. Preferred cations are ammonium (R-^, R4, R5 and R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof. The monoalkanol ammonium compounds of the present invention have R3 equal to C1 -C6 alkanol, R , R5 and R^ equal to hydrogen; dialkanol ammonium compounds of the present invention have R^ and R4 equal to C]-C6 alkanol, R-* and R" equal to hydrogen; trialkanol ammonium compounds of the present invention have R-^, R4 and R^ equal to Ci -Cg alkanol, R^ equal to hydrogen. Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
H3N+CH2CH2OH, H2N+(CH2CH2OH)2, HN+(CH2CH OH)3 .
Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium.
Further regarding the above formula, 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; and w + x + y + z is an integer from 8 to 14.
Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula
Rl R2
I I
CH3CH2(CH2)xCH(CH2)yCH(CH2)zpSO3M wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; R and R^ are each independently hydrogen or C1-C3 alkyl; M is a water soluble cation; x is from 0 to 11 ; y is from 0 to 11 ; z is at least 2; and x + y + z is from 9 to 13; provided Rl and R2 are not both hydrogen.
Preferably, the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight , even more preferably at least 90% by weight of the system, of mid-chain branched primary alkyl sulfates, preferably having Rl and R^ independently hydrogen or methyl, provided Rl and R^ are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 14 to 18, more preferably from 15 to 17, even more preferably from 16 to 17.
Furthermore, preferred surfactant systems are those, which comprise at least about 20%, more preferably at least 60%, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula:
CH3
CH3 (CH2)aCH (CH2)bCH2 OSθ3M
CH3 CH3
CH3 (CH2)dCH (CH2)e CHCH2 OSθ3M or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11 ; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e ^ l ^ d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; whereby, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5.
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 hexadecanol sulfate, 7- methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl hexadecanol sulfate, 11 -methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.
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 sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2, 10-methyl pentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12- methyl pentadecanol sulfate, 2, 13-methyl pentadecanol sulfate, and mixtures thereof.
The following branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
5-methylpentadecylsulfate having the formula:
6-methylpentadecylsulfate having the formula
7-methylpentadecylsulfate having the formula
8-methylpentadecylsulfate having the formula
9-methylpentadecylsulfate having the formula
> S03M
CH,
10-methylpentadecylsulfate having the formula
wherein M is preferably sodium.
The following branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
2,5-dimethylpentadecylsulfate having the formula:
2,6-dimethylpentadecylsulfate having the formula
2,7-dimethylpentadecylsulfate having the formula
2,8-dimethylpentadecylsulfate having the formula
2,9-dimethylpentadecylsulfate having the formula
2,10-dimethylpentadecylsulfate having the formula
wherein M is preferably sodium.
Additional Sulfonate Surfactant
The detergent compositions of the present invention comprise an additional sulfonate surfactant. This surfactant can be any sulfonate surfactant known in the art, not being a sufonate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfonate surfactants are described herein. The ratio of the surfactant system to the additional sulfonate surfactant is preferably from 10:1 to 1 :5, more preferably from 5:1 to 1 :1, even more preferably
Preferred additional sulfonate surfactants for the detergent compositions of the present invention are the salts of C5-C20 linear alkylbenzene sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof. Highly preferred is a Cl 1-C16 linear alkylbenzene sulphonate. Preferred salts are sodium and potassium salts. Alkyl ester sulphonated surfactant are other preferred additional sulfonate surfactants for the detergent compositions of the invention. Preferred are those of the formula
Rl - CH(SO3M) - (A)x - C(O) - OR2
wherein Rl is a C6-C22 hydrocarbyl, R2 is a C^-Cg alkyl, A is a Cg-C22 alkylene, alkenylene, x is 0 or 1 , and M is a cation. Preferred is an -methyl ester sulfonate surfactant. The counterion M is preferably sodium, potassium or ammonium.
The alkyl ester sulphonated surfactant is preferably a -sulpho alkyl ester of the formula above, whereby thus x is 0. Preferably, R is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0. R is preferably ethyl or more preferably methyl.
It can be preferred that the Rl of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.
Additional Sulfate Surfactant
The detergent compositions of the present invention comprise an additional sulfate surfactant. This surfactant can be any sulfate surfactant known in the art, not being a sufate surfactant as defined in the description of the mid-chain branched surfactant system above. Preferred sulfate surfactants are described herein.
The ratio of the surfactant system to the additional sulfate surfactant is preferably from 10:1 to 1 :10, more preferably from 4:1 to 1 :2, even more preferably from 2:1 to 1 :2.
Anionic (mono) sulfate surfactants are preferred additional sulfate surfactants for use in the detergent compositions of the present invention. These include the linear and branched, other than mid-chain branched surfactants of the invention, primary and secondary saturated and unsaturated alkyl sulfates, alkyl ethoxysulfates having an average ethoxylation number of from 0.5 to 15, preferably from 3 to 7, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj- C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides. or glucosides
Primary alkyl mono-sulfate surfactants are preferably selected from the linear and branched primary CjQ-Cig alkyl sulfates, more preferably the C12-C15 chain alkyl sulfates and the C12-C15 linear chain alkyl sulfates.
Preferred secondary alkyl mono-sulfate surfactant are of the formula
R3-CH(SO4M)-R4
wherein R is a C8-C20hydrocycarbyl, R is a hydrocycarbyl and M is a cation.
Alkyl ethoxy mono-sulfate surfactants are preferably selected from the group consisting of the CI Q-CI g alkyl sulphates which have been ethoxylated with from 0.5 to 15 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a 5 alkyl sulfate which has been ethoxylated with from 3 to 9, preferably from 3 to 7, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Preferred salts are sodium and potassium salts.
Additional Sulfate or Sulfonate Surfatcant: Dianionic Surfactants
The additional sulfate surfactant or the additional sulfonate surfactant of the detergent compositions of the invention can also comprise dianionic surfactants, which comprise two anionic groups, each of which can be independently a sulfate or sufonate group, but which can also be a sulfate and a sulfonate group. Therefor, these dianionc surfactants are to be considered either additional sulfate or additional sulfonate surfactants for use in the detegergent compositions of the inevntion, depending on their anionic groups.
The dianionic surfactants, for use in the detergent compositions of the present invention are of the formula:
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C\ to C2g, preferably C3 to C24, most preferably Cg to C20> or hydrogen; A nad B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C] to C2g preferably C1 to C5, most preferably C\ or C2, or a covalent bond, and preferably 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 comprising carboxylate, and preferably sulfate and sulfonate, provided that al least one anionic group X or y is a sulfate or a sulfonate group, z is 0 or preferably 1 ; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
The most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from CJ Q to Cjg, A and B are independently Cj or C2, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
Preferred dianionic surfactants herein include:
(a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulphates, 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 C 20;
(b) 1,4 disulphate compounds, preferably 1,4 C8-C22 straight or branched chain alkyl or alkenyl disulphates, 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 C1 g; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
(c) 1,5 disulphate compounds, preferably 1,5 C9-C23 straight or branched chain alkyl or alkenyl disulphates, 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 C1 g.
It can be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants.
The alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy-linked sulphate or sulphonate group. Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof
The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms. Preferably the structural skeleton comprises only carbon- containing groups and more preferably comprises only hydrocarbyl groups. Most preferably the structural skeleton comprises only straight or branched chain alkyl groups.
The structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching).
A preferred alkoxylated dianionic surfactant has the formula
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C\ to C2 , preferably C3 to C24, most preferably Cg to C20> or hydrogen; A and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length C1 to C2 , preferably Cj to C5, most preferably C1 or C2, or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1 ; 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 sulphate and sulphonate, provided that at least one of X or Y is a sulfate group; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
The most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from C1 Q to C1 g, A and B are independently C1 or C2, n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
The alkoxylated dianionic cleaning agent is typically present at levels of incorporation of from about 0.1 % to about 20%, preferably from about 0.3% to about 15%), most preferably from about 0.5% to about 10% by weight of the bleaching detergent composition.
Preferred alkoxylated dianionic surfactants herein include: ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae:
wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about Ci g; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.
Additional Detergent Components
The detergent compositions in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional detergent components selected from other surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
Other Surfactant
The detergent compositions in accord with the invention can contain one or more other surfactants selected from nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981. When present in the detergent compositions of the invention, the nonionic surfactants are preferably present in low levels, preferably from 0.5% to 20%, more preferably from 1% to 15%, even more preferably from 1.5% to 8% by weight. The ratio of the nonionic surfactants, when present, to the surfactant system is preferably from 5:1 to 1 :20, more preferably from 5:1 to 1 :10, even more preferably from 1 :1 to 1 :10.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propyiene glycol, and the nonionic ethoxylate condensation products with propyiene oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propyiene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms or more preferably 9 to 15 with from 3 to 12 moles of ethylene oxide per mole of alcohol.
Nonionic Polyhydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C\ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive animation reaction; more preferably Z is a glycityl.
Nonionic Fatty Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula: R6cON(R )2 wherein R^ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, Ci -C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)xH, where x is in the range of from l to 3.
Nonionic Alkylpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR4)χNθ(R )2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R-> is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Ci o-Cj alkyl dimethylamine oxide, and Cjo-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2COO~ wherein R is a C -C1 g hydrocarbyl group, each R is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the CJ O-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic Surfactants
Suitable cationic surfactants to be used in the detergent include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cg-Ci 5, preferably C6-C1 Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising 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 US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), - N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
Cationic Mono-Alkoxylated Amine Surfactants
The cationic mono-alkoxylated amine surfactant are preferably of the general formula I:
wherein Rl is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R^ are methyl groups; R is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A is ethoxy and R4 is hydrogen and p is 1, R1 is not a C12-C14 alkyl group.
Preferably the ApR group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are — CH2CH2OH, — CH2CH2CH2OH, — CH2CH(CH3)OH and— CH(CH3)CH2OH, with — CH2CH2OH being particularly preferred. Preferred R groups have have no greater than 10 carbon atoms, or even no greater than 8 or 9 carbon atoms. Preferred Rl groups are linear alkyl groups. Linear Rl groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred. Such a cationic surfactant which is highly preferred has a formula wherein R1 is a Cg-Cjo alkyl group, p is 1, A is ethoxy and R2 and R3 are methyl groups.
Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
wherein R is CJ O-CI g hydrocarbyl and mixtures thereof, especially C10- 14 alkyl, preferably CJQ and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and or i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%), more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition. Cationic Bis-Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general formula II:
wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R4 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 mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
wherein Rl is C^Q-Ci hydrocarbyl and mixtures thereof, preferably CI Q, 12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound Rl is derived from (coconut) C12"C]4 alkyl fraction fatty acids, R2 is methyl and ApR^ and A'qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
wherein Rl is Cjo-Cjg hydrocarbyl, preferably Ci 0-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The levels of the cationic bis-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4%) to 7%, most preferably from 0.5% to 3.0% by weight of the composition.
Optional Surfactants
Suitable optional soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l- heptanoic acid. Certain soaps may also be included as suds suppressors.
Other optional additional anionic surfactants are the carboxylate-based anionic surfactants known in the art and alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1 -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts Water-Soluble Builder Compound
The detergent compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
The detergent compositions of the invention can comprise phosphate-containing builder material, preferably present at a level of from 0.015 to 50%, more preferably from 5% to 30%, more preferably from 8% to 25%, most preferably from 12% to 205 by weight of the composition. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate. . It can be preferred that the compositions are free form phosphate-containing builders
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fiimaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present a t a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1, 2,3 -propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The detergent compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
Na 12 [Alθ2) i2 (Siθ2)i2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(AlO2)g6(SiO2)i06]- 276 H2O.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40%) by weight of the compositions.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
The d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A. Perhydrate Bleaches
An preferred additional components of the detergent composition is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
Organic Peroxyacid Bleaching System
A preferred feature of detergent composition is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O X-C -L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O
X- C - OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%) to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
R3 Y
I I
-O-CH=C-CH=CH2 -O-CH=C-CH=CH2
R3 O Y -O-C=CHR4 , and — N— S ii — C i H— R4
I , ll R3 O
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from
1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Plkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R1 _ — L
wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Cationic Peroxyacid Precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams. Benzoxazin Organic Peroxyacid Precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Organic Peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15%> by weight, more preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
R1 — C- — N — R2 — C- - OOH
1
O R5 O or
R - N — C — R2 — - C — OOH
I I , l
R5 O O
wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP- A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach Catalyst
The bleach system can contain a transition metal containing bleach catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnI^2(u-C)3(l54,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)25 MnH^u- O) i (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(ClO4)2, Mnl V4(u- O)6(l,4,7-triazacyclononane)4-(ClO4)2, Mnι MnIV4(u-O)ι(u-OAc)2_(l,4,7- trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- 1,4,7- triazacyclononane)(OCH3)3_(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, marmitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:
R2 R3
R1-N=C-B-C=N-R4
wherein Rl, R2, R^, and R can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and - bispyridylamine complexes. Highly preferred catalysts include Co(2,2'- bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis- (2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including N4MnIH(u-O)2Mn VN4)+and [Bipy2MnIH(u-
O)2MnIVbipy2]-(ClO4)3.
Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the 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 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.
Enzyme
Another preferred ingredient useful in the detergent is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incoφorated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incoφorated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incoφorated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%) to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001%) to 0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti- redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quaternised ethoxylated (poly) amine clay- soil removal/ anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incoφorated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A- 1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Teφolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incoφoration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Suds Suppressing System
The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci g-C4Q ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propyiene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incoφorated at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propyiene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C 1 g-C \ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C. Polymeric Dye Transfer Inhibiting Agents
The detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
a) Polyamine N-Oxide Polymers
Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
P I (I) Ax
R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general structures : O
O (R^ x -N-tRgJy A
(R3)z or =N-(R1)x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N- oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000. b Copolymers of N-Vinylpyrrolidone and N-Vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
c Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Coφoration, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Coφoration. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d Polyvinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
e Polyvinylimidazole
The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
Optical Brightener
The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. Hydrophilic optical brighteners useful herein include those having the structural formula:
wherein Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxy ethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.
When in the above formula, R1 is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration. Polymeric Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA", 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 compositions.
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 the SRA to be more easily cleaned in later washing procedures.
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. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxy lating 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. Other SRA's include the nonionic end-capped 1 ,2-propylene/polyoxy ethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5- sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or propyiene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1 -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals 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.. Other classes include: (III) anionic terephthalate- based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions preferably contain from about 2% to about 10% by weight of an organic citric acid, preferably citric acid. Also preferably in combination with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incoφorated by reference), can be present in the compositions.
Form of the Compositions
The compositions in accordance with the invention can take a variety of physical forms including liquid but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach, as mentioned above.
However, since preferred detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.
Alternatively, the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
The chlorine-based bleachis such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCT. Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hyposchlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine- based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
The mid-chain branched surfactant system herein, preferably with the additional sulfate and/ or sulfonate surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, preferably not comprising the bleach precursors, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name). A high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of the surfactants, including the mid- chain branched surfactants, is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of 50°C to 80°C is typical.
The mean particle size of the components of granular compositions in accordance with the invention, should preferably be such that no more that 25%> of the particles are greater than 1.8mm in diameter and not more than 25% of the particles are less than 0.25mm in diameter. Preferably the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm in diameter.
The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably 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 200 g/litre, more preferably from 300 g/litre to 1400 g/litre, more preferably from 330g/litre to 1200 gr/litre, most preferably from 380 g/litre to 850 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.
To carry out a measurement, 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.
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. By an effective amount of the detergent composition it is meant from lOg 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.
In a preferred use aspect the detergent composition is formulated such that it is suitable for hand washing.
In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear Ci 2 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C15 linear alkyl sulfate
MES : α-sulpho methylester of C18 fatty acid
CxyEzS : Sodium Cιx-Ci y branched alkyl sulfate condensed with z moles of ethylene oxide MBASX> y : Sodium mid-chain branched alkyl sulfate having an average of x carbon atoms, whereof an average of y carbons comprised in (a) branching unit(s) C 8 SAS : Sodium C14-C18 secondary alcohol sulfate SADExS Sodium C14-C22 alkyl disulfate of formula 2-(R).C4 H7- l,4-(SO4-)2 where R = C100C18, condensed with z moles of ethylene oxide
C45E7 A C14.15 predominantly linear primary alcohol condensed with an average of 7 mole? of ethylene oxide
CxyEz A Cιx.ι y branched primary alcohol condensed with an average of z moles of ethylene oxide
QAS I R2.N+(CH3)2(C2H4OH) with R2 = 50%-60% C9;
40%-50% Cπ
QAS II R1.N+(CH3)(C2H4OH)2 with R1 = C12-C14 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA C 16-C 1 g alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula
Nai2(A102SiO2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5 Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm
Silicate Amoφhous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and q 850μm
MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000
CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename Savinase
Alcalase Proteolytic enzyme of activity 3 AU/g sold by NOVO
Industries A/S Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by
NOVO Industries A S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename Termamyl
60T
Lipase Lipolytic enzyme of activity 1 OOkLU/g sold by NOVO
Industries A/S under the tradename Lipolase
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by
NOVO Industries A/S
PB4 Sodium perborate tetrahydrate of nominal formula
NaBθ2.3H2O.H2θ2
PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2
Percarbonate Sodium Percarbonate of nominal formula
2Na2CO3.3H2O2
NAC-OBS (Nonanamido caproyl) oxybenzene sulfonate in the form of the sodium salt.
NOBS Nonanoyl oxybenzene sulfonate in the form of the sodium salt
DPDA Diperoxydodecanedioic acid
PAP N-phthaloylamidoperoxicaproic acid
NAPAA Nonanoylamido peroxo-adipic acid
NACA 6 nonylamino - 6 oxo - capronic acid.
TAED Tetraacetylethylenediamine
DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest
2060
Photoactivated Sulfonated Zinc or aluminium Phthlocyanine encapsulated
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino- 1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP 1,1 -hydroxy ethane diphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole QEA : bis ((C2H5O)(C2H4θ)n) (CH3) -N+-C6H12-N+-
(CH3) bis ((C2H5O)-(C2H4O)n), wherein n=from 20 to 30 SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propyiene terephtalate) short block polymer Silicone antifoam : Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
In the following Examples all levels are quoted as parts per weight of the composition or % by weight of the composition, as indicated:
Example 1
The following high density granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:
Example 2
The following granular laundry detergent compositions G to I of bulk density 750 g/litre are compositions according to the invention:
Example 3
The following are detergent formulations, according to the present invention where J is a phosphorus-containing detergent composition, K is a zeolite-containing detergent composition and L is a compact detergent composition:
Example 4
The following are detergent formulations according to the present invention:
Example 5
The following are detergent formulations according to the present invention:
Example 6
The following are high density and bleach-containing detergent formulations according to the present invention:
Example 7
The following are high density detergent formulations according to the present invention:
Example 8
The following granular detergent formulations are examples of the present invention.
Example 9
Example 10
The following laundry detergent compositions AQ to AT are prepared in accord with the invention:
Example 11
The following laundry detergent compositions AU to AY are prepared in accord with the invention:
Example 12
The following laundry detergent compositions AZ to Ee are prepared in accord with the invention:

Claims

What is claimed is:
1. A detergent composition comprising
a) at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds of the formula:
A - X - B
wherein:
(I) AD is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, 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 Ci - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the - X - B moiety, to the position of the terminal carbon minus 2 carbons, (the (ω - 2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the AD-X moieties in the above formula is within the range of greater than 14.5 to about 18, preferably from about 15 to about 17;
(II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quats, alkyated/polyhydroxyalkylated quats, alkylated quats, alkylated/polyhydroxylated oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and (III) X is selected from -CH2- and -C(O)-; and
b) at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition of an additional sulfate surfactant; and
c) at least 0.5%, preferably at least 5%, more preferably at least 10%> by weight of the composition of an additional sulfonate surfactant,
whereby the ratio of the surfactant system a) to the surfactant b) is from 20:1 to 1 :20 and the ratio of surfactant system a) to the surfactant c) is from 20: 1 to 1 :10.
2. A detergent composition according to claim 1 wherein the surfactant compounds of the surfactant system a) are of the above formula wherein the AD moiety is a branched primary alkyl moiety having the formula:
R Rl R2
I I I
CH3CH2(CH2)wCH(CH2)xCH(CH2)yCH(CH2)z- wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, Rl, and R2 branching, is from 13 to 19; R, Rl, and R2 are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl, provided R, Rl, and R2 are not all hydrogen and, when z is 0, at least R or Rl 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.
3. A detergent composition according to claim 1 or 2 wherein the surfactant system a) comprises at least 20%, preferably at least 90% by weight of one or more mid-chain branched alkyl sulfates having the formula:
CH3 CH3
CH3 (CH2)dCH (CH2)e CHCH2 OSO3M or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11 , a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10 when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11 when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12 when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13 when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14 when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10 when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11 when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12 whereby the average total number of carbon atoms in the branched primary alkyl moieties is from 14.5 to 17.5.
4. A detergent composition according to claim 3 wherein the average total number of carbon atoms in the branched primary alkyl moieties is from 16 to 17, and the sulfate surfactant is of formula (I).
5. A detergent composition according to any preceding claim wherein the surfactant b)is a C10. ╬╣8 , preferably C12.15 alkyl sulfate surfactant.
6. A detergent composition according to any preceding claim wherein the surfactant c)is a linear Cπ_16 alkyl benzene sulfonate or a α. -methyl ester sulfonate.
7. A detergent composition according to any proceeding claim wherein the ratio of surfactant system a) to surfactant b) is from 4:1 to 1 :2 and of surfactant system a) to surfactant c) is from 5:1 to 1:1
8. A detergent composition according to any preceding claim wherein a nonionic surfactant, preferably a C9.15 primary alcohol ethoxylate containing from 3-12 moles of ethylene oxide per mole of alcohol, is present at a ratio to the anionic surfactant system a)of from 5:1 to 1 :10, preferably 1 :1 to 1 :10.
9. A detergent composition according to claim 7 wherein the nonionic surfactant is present at a level of from 0.5% to 20% by weight of the detergent composition
10. Adetergent composition according to any preceding claim in the form of a solid laundry detergent composition.
EP97913672A 1997-10-10 1997-10-10 A detergent composition Ceased EP1023421A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/018570 WO1999019428A1 (en) 1997-10-10 1997-10-10 A detergent composition

Publications (1)

Publication Number Publication Date
EP1023421A1 true EP1023421A1 (en) 2000-08-02

Family

ID=22261871

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97913672A Ceased EP1023421A1 (en) 1997-10-10 1997-10-10 A detergent composition

Country Status (6)

Country Link
EP (1) EP1023421A1 (en)
AR (1) AR017323A1 (en)
AU (1) AU5080298A (en)
CA (1) CA2305216C (en)
MA (1) MA24899A1 (en)
WO (1) WO1999019428A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6677289B1 (en) * 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
WO2001005923A1 (en) * 1999-07-16 2001-01-25 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
GB0009029D0 (en) * 2000-04-12 2000-05-31 Unilever Plc Laundry wash compositions
CN106221966A (en) * 2016-07-30 2016-12-14 广州芬臣生物科技有限公司 A kind of nanometer Superconcentrated washing sheet and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5940878B2 (en) * 1981-02-10 1984-10-03 花王株式会社 cleaning composition
JPS6013706A (en) * 1983-07-05 1985-01-24 Kao Corp Dispersion of pearl agent
EG21623A (en) * 1996-04-16 2001-12-31 Procter & Gamble Mid-chain branced surfactants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9919428A1 *

Also Published As

Publication number Publication date
CA2305216C (en) 2003-07-08
CA2305216A1 (en) 1999-04-22
AU5080298A (en) 1999-05-03
WO1999019428A1 (en) 1999-04-22
MA24899A1 (en) 2000-04-01
AR017323A1 (en) 2001-09-05

Similar Documents

Publication Publication Date Title
US6482789B1 (en) Detergent composition comprising mid-chain branched surfactants
US6689732B1 (en) Detergent compositions having a specific hydrophobic peroxyacid bleaching system and anionic surfactant
CA2268672C (en) Detergent compositions
EP1023422A1 (en) A detergent composition
EP1021509B1 (en) A detergent composition
WO1999013040A1 (en) Detergent compositions
WO1999013037A1 (en) Bleaching compositions
CA2305216C (en) A detergent composition
WO1999058632A1 (en) Effervescence particle
GB2323371A (en) Detergent compositions
CA2268527A1 (en) Detergent compositions comprising a cellulytic enzyme and a cationic surfactant
CA2336256A1 (en) Builder component
GB2337055A (en) Effervescent particle
EP0934397A1 (en) Detergent compositions
GB2323385A (en) Detergent compositions
CA2331359C (en) Method for dispensing
GB2323382A (en) Detergent compositions
WO2000002436A2 (en) Detergent compositions
GB2323375A (en) Detergent compositions
GB2323376A (en) Detergent compositions
GB2323377A (en) Detergent compositions
GB2323374A (en) Detergent compositions
GB2323381A (en) Detergent compositions
GB2323370A (en) Detergent compositions
GB2323379A (en) Detergent compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000508

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 20040910

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20060428