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WO1999019439A1 - Compositions detergentes legeres liquides ou en gel pour laver la vaisselle comprenant des tensio-actifs ramifies a chaine mediane - Google Patents

Compositions detergentes legeres liquides ou en gel pour laver la vaisselle comprenant des tensio-actifs ramifies a chaine mediane Download PDF

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Publication number
WO1999019439A1
WO1999019439A1 PCT/IB1998/001538 IB9801538W WO9919439A1 WO 1999019439 A1 WO1999019439 A1 WO 1999019439A1 IB 9801538 W IB9801538 W IB 9801538W WO 9919439 A1 WO9919439 A1 WO 9919439A1
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Prior art keywords
integer
alkyl
surfactant
detergent composition
branched
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PCT/IB1998/001538
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English (en)
Inventor
Phillip Kyle Vinson
Thomas Anthony Cripe
William Michael Scheper
Robert Emerson Stidham
Daniel Stedman Connor
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The Procter & Gamble Company
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Priority to JP2000515997A priority Critical patent/JP2001520264A/ja
Publication of WO1999019439A1 publication Critical patent/WO1999019439A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to liquid or gel dishwashing detergent compositions suitable for use in manual dishwashing operations.
  • These liquid detergent compositions contain a surfactant system which comprises mid-chain branched surfactants. Additionally, these compositions optionally comprise other surfactants, suds boosters, viscosity control agents and other adjuvants which in combination serve to impart consumer preferred food soil cleaning and sudsing characteristics to such dishwashing detergent products.
  • LDL Light-duty liquid
  • gel detergent compositions useful for manual dishwashing are well known in the art. Such products are generally formulated to provide a number of widely diverse performance and aesthetics properties and characteristics. First and foremost, liquid or gel dishwashing products must be formulated with types and amounts of surfactants and other cleaning adjuvants that will provide acceptable solubilization and removal of food soils, especially greasy soils, from dishware being cleaned with, or in aqueous solutions formed from, such products.
  • Heavily soiled dishware can present special problems during manual dishwashing operations.
  • Articles such as plates, utensils, pots. pans, crockery and the like may be heavily soiled in the sense that relatively large amounts of food soils and residues may still be found on the dishware at the time such soiled dishware is to be manually washed.
  • Dishware may also be heavily soiled in the sense that food soil residues are especially tenaciously adhered or stuck to the surfaces of the dishware to be cleaned. This can result from the type of food soils present or from the nature of the dishware surfaces involved. Tenacious food soil residues may also result from the type of cooking operations to which the soiled dishware had been subjected. To clean such dishware an appropriate surfactant combination must be employed.
  • LDL or gel compositions will also desirably possess other attributes that enhance the aesthetics or consumer perception of the effectiveness of the manual dishwashing operation.
  • useful hand dishwashing liquids or gels should also employ materials that enhance the sudsing characteristics of the wash solutions formed from such products. Sudsing performance entails both the production of a suitable amount of suds in the wash water initially, as well as the formation of suds which last well into the dishwashing process.
  • Hand dishwashing liquids or gels should also employ materials that enhance product phase stability at low temperatures. Lack of phase stability can lead to unacceptable rheological and aesthetic properties as well as to performance issues. Such low temperatures can be encountered in warehouses, in the consumer's garage, in the consumer's automobile, during street vending, on the kitchen window sill, and the like. Further, hand dishwashing liquids and gels should employ materials that enhance the dissolution, or rate of product mixing, with water. Further, hand dishwashing liquids and gels should employ materials that enhance the tolerance of the system to hardness, especially to avoid the precipitation of the calcium salts of anionic surfactants. Precipitation of the calcium salts of anionic surfactants is known to cause suppression of suds and irritation to the skin.
  • mid-chain branched surfactants provide significantly improved tolerance to hardness, significantly improved low temperature stability of the finished product and significantly improved rates of mixing of the product with water.
  • the present invention relates to aqueous light-duty liquid or gel detergent compositions having especially desirable soil removal and sudsing performance when such compositions are used to clean heavily soiled dishware.
  • Such compositions comprise A) a surfactant system comprising a branched surfactant mixture which comprises mid-chain branched and linear surfactant compounds; B) from about 0.1 to about 8% of an alkyl dimethyl amine oxide and from about 0.05 to about 2% of Magnesium ions; and C) from about 30% to about 95% of an aqueous liquid carrier.
  • the branched surfactant mixture comprises at least about 10%, preferably at least about 20%, more preferably at least about 30% and most preferably at least about 50%, by weight of the surfactant system.
  • the branched surfactant mixture comprises mid- chain branched and linear surfactant compounds, the linear compounds exceeding at least 25% and less than about 70%, preferably greater than 25% and less than about 60% and most preferably greater than 25% and less than about 50%, by weight of the branched surfactant mixture and the mid-chain branched compounds being of the formula:
  • A is a hydrophobic moiety having from about 9 to about 18, preferably from about 11 to about 17 and most preferably from about 1 1 to about 15 total carbons.
  • the carbons are divided between a longest chain and at least one short chain, the longest chain being in the range of from about 9 to about 17 carbon atoms.
  • B is a hydrophilic moiety selected from the group consisting of OSO3M, (EO/PO)mOSO3M and mixtures thereof.
  • EO/PO are alkoxy moieties selected from the group consisting of ethoxy, propoxy, and mixtures thereof, and m is at least about 0.01 to about 30.
  • the average total number of carbon atoms in the A D moiety in the branched surfactant mixture defined above should be within the range of greater than about 12 to about 14.5, preferably greater than about 12 to about 14 and most preferably greater than about 12 to about 13.5.
  • the surfactant system of the liquid detergent compositions of the present invention can optionally comprise additional surfactants such as anionics and nonionics.
  • the anionic surfactant component essentially comprises alkyl ether sulfates containing from about 9 to 18 carbon atoms in the alkyl group. These alkyl ether sulfates also contain from about 1 to 12 moles of ethylene oxide per molecule.
  • the nonionic surfactant component essentially comprises Cg-Ci g polyhydroxy fatty acids amides. In the nonionic surfactant components such polyhydroxy fatty acids amides may also be combined with from about 0.2 % to 2% of the composition of a nonionic co- surfactant.
  • This nonionic co-surfactant is selected from Cg-Cj g alcohol ethoxylates having from about 1 to 30 moles of ethylene oxide, ethylene oxide-propylene oxide block co-polymer surfactants and combinations of these nonionic co-surfactants.
  • compositions of the present invention can also optionally comprise a suds booster/stabilizer selected from betaine surfactants, alkanol fatty acid amides, amine oxide semipolar nonionic surfactants and Cg-C22 alkylpolyglycosides. Combinations of these suds booster/stabilizers may also be utilized.
  • a suds booster/stabilizer selected from betaine surfactants, alkanol fatty acid amides, amine oxide semipolar nonionic surfactants and Cg-C22 alkylpolyglycosides. Combinations of these suds booster/stabilizers may also be utilized.
  • the light-duty liquid composition can optionally comprise from about 0.2% to 2% of a hydroxypropyl methylcellulose polymer that is sufficient to impart to the composition a Brookfield viscosity from about 500 to 3500 cps at 25° C.
  • the light-duty liquid or gel dishwashing detergent compositions of the present invention contain three essential components. These components are:
  • a surfactant system which comprises certain mid-chain branched alkyl surfactants and certain nonionic surfactants;
  • compositions herein (3) an aqueous liquid carrier.
  • optional ingredients can also be added to compliment the performance, rheological and/or aesthetics characteristics of the compositions herein.
  • compositions of the present invention refers to those compositions which are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
  • concentrations and ratios are on a weight basis unless otherwise specified.
  • the surfactant system of the subject liquid detergent compositions comprises at least about 10%, preferably at least about 20%, more preferably at least about 30% and most preferably at least about 50%, by weight of a branched surfactant mixture.
  • the branched surfactant mixture comprises mid-chain branched and linear surfactant compounds, the linear compounds exceeding at least 25% and less than about 70%, preferably greater than 25% and less than about 60% and most preferably greater than 25% and less than about 50%, by weight of the branched surfactant mixture and the mid- chain branched compounds being of the formula:
  • A" is a hydrophobic moiety having from about 10 to about 18, preferably from about 11 to about 17 and most preferably from about 11 to about 15 total carbons.
  • the carbons are divided between a longest chain and at least one short chain, the longest chain being in the range of from about 9 to about 17 carbon atoms.
  • B is a hydrophilic moiety selected from the group consisting of OSO3M, (EO/PO)mOSO3M and mixtures thereof.
  • EO/PO are alkoxy moieties selected from the group consisting of ethoxy, propoxy, and mixtures thereof, and m is at least about 0.01 to about 30.
  • the average total number of carbon atoms in the A D moiety in the branched surfactant mixture defined above should be within the range of greater than 12 to about 14.5, preferably greater than about 12 to about 14 and most preferably greater than about 12 to about 13.5.
  • the "total" number of carbon atoms as used herein is intended to mean the number of carbon atoms in the longest chain, i.e. the backbone of the molecule, plus the number of carbon atoms in all of the short chains, i.e. the branches.
  • the branched surfactants of the present invention can preferably comprise compounds of the above formula wherein the A D moiety is a branched alkyl moiety having the formula:
  • R, Rl, and R ⁇ are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl.
  • 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 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10 and w + x + y + z is from 3 to 10.
  • an especially preferred branched surfactant for use in the detergent compositions of the present invention comprises an A D moiety which is characterized as having one of the two formulas below and mixtures thereof:
  • mid-chain branched surfactant compositions of the present invention may comprise one or more mid-chain branched primary alkyl sulfate surfactants having the formula:
  • the branched surfactant mixtures of the present invention comprise molecules having a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom). These alkyl chain backbones comprise from about 10 to about 18 carbon atoms; and further the molecules comprise a branched primary alkyl moiety or moieties having at least about 1, but not more than 3, carbon atoms.
  • the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties of from about 12 to about 14.5.
  • the present invention mixtures comprise at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 9 carbon atoms or more than 17 carbon atoms, and the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 12 to about 14.5, preferably greater than about 12 to about 14 and most preferably greater than about 12 to about 13.5.
  • a C14 total carbon primary alkyl sulfate surfactant having 11 carbon atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, R and/or R ⁇ ) whereby total number of carbon atoms in the molecule is 14.
  • the C14 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units.
  • R, Rl, and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R*, and R ⁇ are not all hydrogen. Further, when z is 0, at least R or R! is not hydrogen.
  • surfactant compositions the above formula does not include molecules wherein the units R, Rl, and R ⁇ are all hydrogen (i.e., linear non-branched primary alkyl sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non- branched primary alkyl sulfate.
  • this linear non-branched primary alkyl sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite one or more mid-chain branched primary alkyl sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkyl sulfate may be admixed into the final product formulation.
  • non-sulfated mid-chain branched alcohol may comprise some amount of the present invention compositions. Such materials may be present as the result of incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkyl sulfate surfactant according to the present invention.
  • 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 wherein R2, R * *, R5 and R ⁇ are independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, Ci -Cg alkanol. C1 -C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof.
  • Preferred cations are ammonium (R2. R ⁇ , R5 and R equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
  • the monoalkanol ammonium compounds of the present invention have R2 equal to Cj-Cg alkanol, R4, R5 and R ⁇ equal to hydrogen; dialkanol ammonium compounds of the present invention have R2 and R ⁇ equal to Cj-Cg alkanol, R ⁇ and R ⁇ equal to hydrogen; trialkanol ammonium compounds of the present invention have R2, R4 and R ⁇ equal to C ⁇ -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:
  • M is sodium, potassium and the C2 alkanol ammonium salts listed above; the most M preferred is sodium.
  • the preferred surfactant mixtures of the present invention have at least about 10%, more preferably at least about 20%, even more preferably at least about 30% and most preferably at least about 50% by weight, of the mixture of one or more branched primary alkyl sulfates having the formula:
  • R* and R ⁇ are each independently hydrogen or C1 -C3 alkyl.
  • M is a water soluble cation; x is from 0 to 10; y is from 0 to 10; z is from 0 to 10 and x + y + z is from 4 to 10.
  • R* and R ⁇ are not both hydrogen. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary alkyl sulfates wherein x + y is equal to 6 and z is at least 1.
  • the mixtures of surfactant comprise at least 5% of a mid chain branched primary alkyl sulfate having R* and R2 independently hydrogen or methyl.
  • R ⁇ and R2 are not both hydrogen, and x + y is equal to 5, 6 or 7 and z is at least 1.
  • the mixtures of surfactant comprise at least 20% of a mid chain branched primary alkyl sulfate having R ⁇ and R2 independently hydrogen or methyl, provided R! and R2 are not both hydrogen; x + y is equal to 5, 6 or 7 and z is at least 1.
  • Preferred mid-chain branched primary alkyl sulfate surfactants for use in the detergent compositions defined herein are selected from the group of compounds having the formula:
  • M represents one or more cations; a, b, d, and e are integers, a+b is from about 6 to about 13, d+e is from about 4 to about 11.
  • the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than about 12 to about 14.5.
  • Especially preferred mid-chain branched surfactants are those comprising a mixture of compounds having the general formulas from Groups I and II, wherein the molar ratio of compounds according to Group I to Group II is greater than 4:1, preferably greater than 5 : 1 and most preferably greater than 9:1.
  • the present invention surfactant composition may comprise a mixture of linear and branched surfactants wherein the branched primary alkyl sulfates have the formula:
  • the total number of carbon atoms per molecule, including branching, is from 10 to 17, and the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than about 12 to about 14.5.
  • R, Rl, and R are each independently selected from hydrogen and C1-C3 alkyl, provided R, R 1 , and R are not all hydrogen.
  • M is a water soluble cation; w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10; and w + x + y + z is from 3 to 10.
  • R2 when R2 is a C1 -C3 alkyl the ratio of surfactants having z equal to 0 to surfactants having z of 1 or greater is at least about 1:1, preferably at least about 1 :5, more preferably at least about 1 :10, and most preferably at least about 1 :20. Also preferred are surfactant compositions, when R2 is a C1-C3 alkyl, comprising less than about 20%, preferably less than 10%, more preferably less than 5%, most preferably less than 1%, of branched primary alkyl sulfates having the above formula wherein z equals 0.
  • Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl dodecanol sulfate, 4-methyl dodecanol sulfate, 5-methyl dodecanol sulfate, 6-methyl dodecanol sulfate, 7-methyl dodecanol sulfate, 8-methyl dodecanol sulfate, 9-methyl dodecanol sulfate, 10-methyl dodecanol sulfate, 3-methyl tridecanol sulfate, 4-methyl tridecanol sulfate, 5-methyl tridecanol sulfate, 6-methyl tridecanol sulfate, 7-methyl tridecanol sulfate, 8-methyl tridecanol sulfate, 9-methyl tridecanol sulfate, 10-methyl tridecanol sulfate, 1 1 -methyl tridecanol sulf
  • Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-dimethyl undecanol sulfate, 2,4-dimethyl undecanol sulfate, 2,5- dimethyl undecanol sulfate, 2.6-dimethyl undecanol sulfate, 2,7-dimethyl undecanol sulfate, 2,8-dimethyl undecanol sulfate, 2,9-dimethyl undecanol sulfate, 2,3-dimethyl dodecanol sulfate, 2,4-dimethyl dodecanol sulfate, 2,5-dimethyl dodecanol sulfate, 2,6- dimethyl dodecanol sulfate, 2.7-dimethyl dodecanol sulfate, 2,8-dimethyl dodecanol sulfate, 2,9-dimethyl dodecanol sulfate
  • branched primary alkyl sulfates comprising 13 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
  • branched primary alkyl sulfates comprising 14 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
  • M is preferably sodium.
  • M is preferably sodium.
  • mid-chain branched surfactant components of the present invention may comprise one or more (preferably a mixture of two or more) mid-chain branched primary alkyl alkoxylated sulfates having the formula:
  • the surfactant mixtures of the present invention comprise molecules having a linear primary alkoxylated sulfate chain backbone (i.e., the longest linear carbon chain which includes the alkoxy-sulfated carbon atom). These alkyl chain backbones comprise from about 9 to about 18 carbon atoms; and further the molecules comprise a branched primary alkyl moiety or moieties having at least about 1, but not more than 3, carbon atoms.
  • the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties of from about 12 to about 14.5.
  • the present invention mixtures comprise at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 9 carbon atoms or more than 17 carbon atoms, and the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 12 to about 14.5, preferably greater than about 12 to about 14 and most preferably greater than about 12 to about 13.5.
  • a C14 total carbon primary alkyl sulfate surfactant having 11 carbon atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, R and/or R2) whereby total number of carbon atoms in the molecule is 14.
  • the C14 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units.
  • R, Rl, and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, Rl, and R2 are not all hydrogen. Further, when z is 0, at least R or Rl is not hydrogen.
  • surfactant components according to the above formula do not include molecules wherein the units R, Rl, and R2 are all hydrogen (i.e., linear non-branched primary alkoxylated sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-branched primary alkoxylated sulfate.
  • this linear non- branched primary alkoxylated sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite mid-chain branched primary alkoxylated sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkoxylated sulfate may be admixed into the final product formulation.
  • mid-chain branched alkyl sulfate may be present in the compositions. This is typically the result of sulfation of non- alkoxylated alcohol remaining following incomplete alkoxylation of the mid-chain branched alcohol used to prepare the alkoxylated sulfate useful herein. It is to be recognized, however, that separate addition of such mid-chain branched alkyl sulfates is also contemplated by the present invention compositions.
  • non-sulfated mid-chain branched alcohol may comprise some amount of the present invention alkoxylated sulfate-containing compositions.
  • Such materials may be present as the result of incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkoxylated sulfate surfactant according to the present invention.
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within che range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5.
  • the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m.
  • the preferred surfactant mixtures of the present invention have at least about 10%, more preferably at least about 20%, even more preferably at least about 30% and most preferably at least about 50% by weight, of the mixture of one or more mid-chain branched primary alkyl alkoxylated sulfates having the formula:
  • Rl and R2 are each independently hydrogen or -C3 alkyl.
  • M is a water soluble cation; x is from 0 to 10; y is from 0 to 10; z is from 0 to 10 and x + y + z is from 4 to 10.
  • R* and R2 are not both hydrogen.
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30. more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary alkyl alkoxy sulfates wherein x + y is equal to 6 and z is at least 1.
  • the mixtures of surfactant comprise at least 5% of a mid chain branched primary alkyl sulfate having Rl and R2 independently hydrogen or methyl, provided Rl and R2 are not both hydrogen; x + y is equal to 5, 6 or 7 and z is at least 1. More preferably the mixtures of surfactant comprise at least 20% of a mid chain branched primary alkyl sulfate having Rl and R2 independently hydrogen or methyl, provided R* and R2 are not both hydrogen; x + y is equal to 5, 6 or 7 and z is at least 1.
  • Preferred mixtures of mid-chain branched primary alkyl alkoxylated sulfate and linear alkyl alkoxylated sulfate surfactants comprise at least about 5 % by weight of one or more mid-chain branched alkyl alkoxylated sulfates having the formula:
  • M represents one or more cations, a, b, d, and e are integers, wherein a+b is from about 6 to about 13, d+e is from about 4 to about 11.
  • the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than about 12 to about 14.5 and EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about
  • mid-chain branched surfactants are those comprising a mixture of compounds having the general formulas from Groups I and II, wherein the molar ratio of compounds according to Group I to Group II is greater than about 4:1, preferably greater than about 5:1 and most preferably greater than about 9:1.
  • the present invention surfactant composition may comprise a mixture of linear and branched surfactants wherein the branched primary alkyl alkoxylated sulfates has the formula:
  • the total number of carbon atoms per molecule, including branching, is from 10 to 17, and the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than about 12 to about 14.5.
  • R, R1 , and R2 are each independently selected from hydrogen and C1-C3 alkyl, provided R, R*, and R are not all hydrogen.
  • M is a water soluble cation; w is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10; z is an integer from 0 to 10; and w + x + y + z is from 3 to 10.
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5.
  • R2 is a C1-C3 alkyl the ratio of surfactants having z equal to 0 to surfactants having z of 1 or greater is at least about 1 :1, preferably at least about 1 :5, more preferably at least about 1 :10, and most preferably at least about 1 :20.
  • surfactant compositions when R2 is a C1-C3 alkyl, comprising less than about 20%, preferably less than 10%, more preferably less than 5%, most preferably less than 1%, of branched primary alkyl alkoxylated sulfate having the above formula wherein z equals 0.
  • Preferred mono-methyl branched primary alkyl ethoxylated sulfates are selected from the group consisting of: 3-methyl dodecanol ethoxylated sulfate, 4-methyl dodecanol ethoxylated sulfate, 5-methyl dodecanol ethoxylated sulfate, 6-methyl dodecanol ethoxylated sulfate, 7-methyl dodecanol ethoxylated sulfate, 8-methyl dodecanol ethoxylated sulfate, 9-methyl dodecanol ethoxylated sulfate, 10-methyl dodecanol ethoxylated sulfate, 3-methyl tridecanol ethoxylated sulfate, 4-methyl tridecanol ethoxylated sulfate, 5-methyl tridecanol ethoxylated sulfate, 6-methyl tridecanol eth
  • Preferred di-methyl branched primary alkyl ethoxylated sulfates selected from the group consisting of: 2,3-dimethyl undecanol ethoxylated sulfate, 2,4-dimethyl undecanol ethoxylated sulfate, 2,5-dimethyl undecanol ethoxylated sulfate, 2,6-dimethyl undecanol ethoxylated sulfate, 2,7-dimethyl undecanol ethoxylated sulfate, 2,8-dimethyl undecanol ethoxylated sulfate, 2,9-dimethyl undecanol ethoxylated sulfate, 2,3-dimethyl dodecanol ethoxylated sulfate, 2,4-dimethyl dodecanol ethoxylated sulfate, 2,5-dimethyl dodecanol ethoxylated sulfate,
  • Formulation of the alkyl halide resulting from the first hydrogenation step yields alcohol product, as shown in the scheme.
  • This can be alkoxylated using standard techniques and/or sulfated using any convenient sulfating agent, e.g., chlorosulfonic acid, SO3/air, or oleum, to yield the final branched primary alkyl surfactant.
  • sulfating agent e.g., chlorosulfonic acid, SO3/air, or oleum
  • Such extension can, for example, be accomplished by reaction with ethylene oxide. See “Grignard Reactions of Nonmetallic Substances", M.S. Kharasch and O. Reinmuth, Prentice-Hall, N.Y., 1954; J. Org. Chem., J.
  • PBr3 halogenation of the alcohol from formulation or ethoxylation can be used to accomplish an iterative chain extension.
  • the preferred mid-chained branched primary alkyl alkoxylated sulfates (as well as the polyoxyalkylenes and alkyl sulfates, by choosing to only alkoxylate or sulfate the intermediate alcohol produced) of the present invention can also be readily prepared as follows:
  • a conventional bromoalcohol is reacted with triphenylphosphine followed by sodium hydride, suitably in dimethylsulfoxide/tetrahydrofuran, to form a Wittig adduct.
  • the Wittig adduct is reacted with an alpha methyl ketone, forming an internally unsaturated methyl-branched alcoholate. Hydrogenation followed by alkoxylation and/or sulfation yields the desired mid-chain branched primary alkyl surfactant.
  • the Wittig approach does not allow the practitioner to extend the hydrocarbon chain, as in the Grignard sequence, the Wittig typically affords higher yields. See Agricultural and Biological Chemistry, M. Horiike et al., vol.
  • the mid-chain branched primary alkyl surfactants may, in addition be synthesized or formulated in the presence of the conventional homologs, for example linear homologues or any of those which may be formed in an industrial process which produces 2-alkyl branching as a result of hydroformylation.
  • said surfactant mixtures of the present invention comprise at least 1 mid-chain branched primary alkyl surfactant, preferably at least 2, more preferably at least 5, most preferably at least 8.
  • Particularly suitable for preparation of certain surfactant mixtures of the present invention are "oxo" reactions wherein a branched chain olefin is subjected to catalytic isomerization and hydroformylation prior to alkoxylation and/or sulfation.
  • the preferred processes resulting in such mixtures utilize fossil fuels as the starting material feedstock.
  • Preferred processes utilize Oxo reaction on olefins (alpha or internal) with a limited amount of branching.
  • Suitable olefins may be made by dimerization of linear alpha or internal olefins, by controlled oligomerization of low molecular weight linear olefins, by skeletal rearrangement of detergent range olefins, by dehydrogenation/skeletal rearrangement of detergent range paraffins, or by Fischer-Tropsch reaction. These reactions will in general be controlled to:
  • the linear olefin content can be controlled in various ways, e.g., by controlling the extent to which skeletal rearrangement is allowed to proceed or by blending of branched and linear olefins.
  • the suitable olefins can undergo Oxo reaction to give primary alcohols either directly or indirectly through the corresponding aldehydes.
  • an Oxo catalyst is normally used which is capable of prior pre-isomerization of internal olefins primarily to alpha olefins. While a separately catalyzed (i.e. non-Oxo) internal to alpha isomerization could be effected, this is optional.
  • a preferred embodiment of the surfactant mixtures of the present invention involves those materials derived from commercial processes wherein an olefin-rich feedstock containing branched chain olefins, linear olefins and other olefins, e.g., olefins containing cyclical structures, substituted cyclical olefins, and the like, is subjected to carbon monoxide and hydrogen in the presence of a catalytic amount of a hydroformylation catalyst prior to alkoxylation and/or sulfation
  • the olefin-rich feedstock is obtained by subjecting a synthesis gas comprising carbon monoxide (CO) and hydrogen (H2) to Fischer-Tropsch reaction conditions in the presence of an iron-based, a cobalt-based, or an iron/cobalt-based Fischer-Tropsch catalyst.
  • the average total carbon atoms of the branched primary alkyl surfactants herein can be calculated from the hydroxyl value of the precursor fatty alcohol mix or from the hydroxyl value of the alcohols recovered by extraction after hydrolysis of the alcohol sulfate mix according to common procedures, such as outlined in "Bailey's Industrial Oil and Fat Products", Volume 2, Fourth Edition, edited by Daniel Swern, pp. 440-441.
  • the light duty dishwashing detergent compositions herein further contain from about 30% to 95% of an aqueous liquid carrier in which the other essential and optional compositions components are dissolved, dispersed or suspended. More preferably the aqueous liquid carrier will comprise from about 50% to 65% of the compositions herein.
  • the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature and which may also serve some other function besides that of a simple filler. Such materials can include, for example, hydrotropes and solvents. Due in large part to the properties of the mid-chain branched surfactants of the present invention, the water in the aqueous liquid carrier can have a hardness level of at least about 15 gpg or more ("gpg" is a measure of water hardness that is well known to those skilled in the art, and it stands for "grains per gallon").
  • the aqueous liquid carrier may comprise one or more materials which are hydrotropes.
  • Hydrotropes suitable for use in the compositions herein include the C1-C3 alkyl aryl sulfonates, Cg-Cj2 alkanols, Cj-Cg carboxylic sulfates and sulfonates, urea, Cj-Cg hydrocarboxylates, C1-C4 carboxylates, C2-C4 organic diacids and mixtures of these hydrotrope materials.
  • the liquid detergent composition of the present invention preferably comprises from about 0.5% to 8%, by weight of the liquid detergent composition of a hydrotrope selected from alkali metal and calcium xylene and toluene sulfonates.
  • Suitable C1-C3 alkyl aryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulfonates and mixtures thereof.
  • Suitable Cj-Cg carboxylic sulfate or sulfonate salts are any water soluble salts or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulfate or sulfonate and have at least one carboxylic group.
  • the substituted organic compound may be cyclic, acylic or aromatic, i.e. benzene derivatives.
  • Preferred alkyl compounds have from 1 to 4 carbon atoms substituted with sulfate or sulfonate and have from 1 to 2 carboxylic groups.
  • hydrotrope examples include sulfosuccinate salts, sulfophthalic salts, sulfoacetic salts, m- sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or potassium salts as disclosed in U.S. 3,915,903.
  • Suitable C1 -C4 hydrocarboxylates and C1-C4 carboxylates for use herein include acetates and propionates and citrates.
  • Suitable C2-C4 diacids for use herein include succinic, glutaric and adipic acids.
  • hydrotrope examples include Cg-Cj2 alkanols and urea.
  • Preferred hydrotropes for use herein are sodium, potassium, calcium and ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and mixtures thereof. Most preferred are sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof. These preferred hydrotrope materials can be present in the composition to the extent of from about 0.5% to 8% by weight.
  • a variety of water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like may be used as part of the aqueous liquid carrier. Particularly preferred are the C1-C4 alkanols.
  • Such solvents can be present in the compositions herein to the extent of from about 1% to 8%.
  • Preferred optional ingredients in the dishwashing compositions herein include, anionic and nonionic surfactants, ancillary surfactants, calcium and/or magnesium ions, enzymes such as protease, and a stabilizing system for the enzymes. These and other optional ingredients are described as follows:
  • compositions herein can contain from about 5% to 40% of an anionic surfactant component. More preferably the anionic surfactant component comprises from about 15% to 35% of the compositions herein.
  • the anionic surfactant component preferably comprises alkyl sulfates and alkyl ether sulfates derived from conventional alcohol sources, e.g., natural alcohols, synthetic alcohols such as those sold under the trade name of NEODOLTM, ALFOLTM, LIALTM, LUTENSOLTM and the like.
  • Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates. These ethoxylated alkyl sulfates are those which correspond to the formula:
  • R' is a Cg-Cjg alkyl group, n is from about 0.01 to 6, and M is a salt-forming cation.
  • R' is C JO-16 alkyl, n is from about 0.01 to 4, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is Cl2"Cl6 > n s fr° m about 0.01 to 3 and M is sodium.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C15 linear alkylbenzenesulphonates, C -C22 primary or secondary alkanesulphonates, Cg-C22 olefin sulphonates. sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • alkyl ester sulfonates are desirable because they can be made with renewable, non- petroleum resources.
  • Preparation of the alkyl ester sulfonate surfactant component can be effected according to known methods disclosed in the technical literature. For instance, linear esters of C -C20 carboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323- 329. Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
  • Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g. tetramethyl- ammonium and dimethyl piperdinium. and cations derived from alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine. Especially preferred are the methyl ester sulfonates wherein the alkyl group is Ci2-C ⁇ g.
  • Secondary detersive surfactant can be selected from the group consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof.
  • the present detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning applications, particularly including dishwashing.
  • the particular surfactants used can therefore vary widely depending upon the particular end-use envisioned. Suitable secondary surfactants are described below.
  • Nonionic Surfactants In addition to the branched surfactant mixture disclosed above, the compositions herein can also contain from about 3% to 10% of a certain type of nonionic surfactant component. More preferably, the nonionic surfactant component will comprise from about 4% to 6% of the compositions herein.
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference.
  • Exemplary, non-limiting classes of useful nonionic surfactants include: alkyl dialkyl amine oxide, alkyl ethoxylate, alkanoyl glucose amide, alkyl betaines, and mixtures thereof.
  • Nonionic surfactant which is present in the compositions herein comprises the Cg-Cjg, preferably Cjo-Cjg, polyhydroxy fatty acid amides. These materials are more fully described in Pan Gosselink; U.S Patent 5,332,528; Issued July 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides have a general structure of the formula:
  • R is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof;
  • R2 is Cg-Ci g hydrocarbyl;
  • Z is a polyhydroxylhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • surfactants include the Cjo-Cig N- methyl, or N-hydroxypropyl, glucamides.
  • the N-propyl through N-hexyl C ⁇ - i glucamides can be used for lower sudsing performance.
  • Polyhydroxy fatty acid amides will preferably comprise from about 1% to 5% of the compositions herein.
  • the polyhydroxy fatty acid amides hereinbefore described may be combined with certain other types of nonionic co-surfactants. These other types include ethoxylated alcohols and ethylene oxide-propylene oxide block co-polymer surfactants, as well as combinations of these nonionic co-surfactant types.
  • nonionic surfactants for use herein include: the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols.
  • the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Corporation; and Triton® X-45, X-l 14, X-100, and X-102, all marketed by the Rohm & Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
  • Ethoxylated alcohol surfactant materials useful in the nonionic surfactant component herein are those which correspond to the general formula:
  • Rl is a Cg-Cjg alkyl group and n ranges from about 5 to 15.
  • R is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 9 to 12 carbon atoms.
  • the ethoxylated fatty alcohols will contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 8 to 12 ethylene oxide moieties per molecule.
  • the ethoxylated fatty alcohol nonionic co-surfactant will frequently have a hydrophilic- lipophilic balance (HLB) which ranges from about 6 to 15, most preferably from about 10 to 15.
  • HLB hydrophilic- lipophilic balance
  • fatty alcohol ethoxylates useful as the nonionic co-surfactant component of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the tradenames Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12- 13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91- 5 is an ethoxylated CQ-CJ ⁇ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohol nonionic surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C ⁇ ⁇ to C ⁇ 5 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol ethoxylate nonionics useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
  • Ethoxylated alcohol nonionic co-surfactants will frequently comprise from about 0.2% to 4% of the compositions herein. More preferably, such ethoxylated alcohols will comprise from about 0.5% to 1.5% of the compositions.
  • nonionic co-surfactant suitable for use in combination with the nonionic surfactant component herein comprises the ethylene oxide-propylene oxide block co-polymers that function as polymeric surfactants.
  • block co-polymers comprise one or more groups which are hydrophobic and which contain mostly ethylene oxide moieties and one or more hydrophobic groups which contain mostly propylene oxide moieties.
  • groups are attached to the residue of a compound that contained one or more hydroxy groups or amine groups.
  • Such polymeric surfactants have a molecular weight ranging from about 400 to 60,000.
  • Preferred ethylene oxide-propylene oxide polymeric surfactants are those in which propylene oxide is condensed with an amine, especially a diamine, to provide a base that is then condensed with ethylene oxide. Materials of this type are marketed under the tradename Tetronic®. Similar structures wherein the ethylene diamine is replaced with a polyol such as propylene glycol are marketed under the tradename "Pluronic®”. Preferred ethylene oxide-propylene oxide (EO-PO) polymeric surfactants have an HLB which ranges from about 4 to 30, more preferably about 10 to 20. The ethylene oxide-propylene oxide block co-polymers used herein are described in greater detail in Pancheri Mao; U.S. Patent 5,167,872; Issued December 2, 1992. This patent is incorporated herein by reference.
  • Ethylene oxide-propylene oxide block co-polymers will frequently be present to the extent of from about 0.1% to 2% of the compositions herein. More preferably, these polymeric surfactant materials will comprise from about 0.2% to 0.8% of the compositions herein.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, terra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
  • the preferred alkylpolyglycosides have the formula R2 ⁇ (C n H 2n O) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3- , 4- and/or 6-position, preferably predominantly the 2-position.
  • compositions herein can further include from about 2% to 8%, preferably from about 3% to 6%, of a suds booster or stabilizer component such as betaine surfactants, fatty acid alkanol amides, amine oxide semi-polar nonionic surfactants, and Cg_22 alkyl polyglycosides. Combinations of these suds boosters/stabilizers can also be used.
  • a suds booster or stabilizer component such as betaine surfactants, fatty acid alkanol amides, amine oxide semi-polar nonionic surfactants, and Cg_22 alkyl polyglycosides.
  • Betaine surfactants useful as suds boosters herein have the general formula:
  • R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amino or ether linkages; each R is an alkyl group containing from 1 to about 3 carbon atoms; and R is an alkylene group containing from 1 to about 6 carbon atoms.
  • betaines dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
  • Other suitable amidoalkylbetaines are disclosed in U.S. Patent Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, all of which are incorporated herein by reference.
  • Alkanol amide surfactants useful as suds boosters herein include the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms. These materials are represented by the formula:
  • R ⁇ is a saturated or unsaturated, hydroxy-free aliphatic hydrocarbon group having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1.
  • Specific examples of such amides are monoethanol amine coconut fatty acid amide and diethanolamine dodecyl fatty acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanolamides and diethanolamides of C fatty acids are preferred.
  • Amine oxide semi-polar nonionic surfactants useful as suds boosters/stabilizers comprise compounds and mixtures of compounds having the formula:
  • R is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R and R are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2- hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10.
  • Particularly preferred are amine oxides of the formula:
  • R is a C alkyl and R and R are methyl or ethyl.
  • surfactants suitable for use as suds boosters/stabilizers in the compositions herein are the nonionic fatty alkylpolyglycosides. Such materials have the formula:
  • Z is derived from glucose
  • R is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 8 to 22, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, y is from 0 to 10, preferably 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
  • U.S Patents 4,393,203 and 4,732.704 incorporated herein by reference, describe these alkyl polyglycoside surfactants.
  • the dishwashing detergent compositions herein can also contain from about 0.2% to 5% of a thickening agent. More preferably, such a thickener will comprise from about 0.5% to 2.5% of the compositions herein.
  • Thickeners are typically selected from the class of cellulose derivatives. Suitable thickeners include hydroxy ethyl cellulose, hydroxyethyl methyl cellulose, carboxy methyl cellulose. Quatrisoft LM200, and the like. A preferred thickening agent is hydroxypropyl methylcellulose.
  • the hydroxypropyl methylcellulose polymer has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt.% aqueous solution at 25°C. (ADTMD2363) of about 50,000 to about 100,000 cps.
  • An especially preferred hydroxypropyl cellulose polymer is Methocel® J75MS-N wherein a 2.0 wt.% aqueous solution at 25°C. has a viscosity of about 75,000 cps.
  • Especially preferred hydroxypropyl cellulose polymers are surface treated such that the hydroxypropyl cellulose polymer will ready disperse at 25 °C. into an aqueous solution having a pH of at least about 8.5.
  • the hydroxypropyl methylcellulose polymer When formulated into the dishwashing detergent compositions of the present invention, the hydroxypropyl methylcellulose polymer should impart to the detergent composition a Brookfield viscosity of from about 500 to 3500 cps at 25°C. More preferably, the hydroxypropyl methylcellulose material will impart a viscosity of from about 1000 to 3000 cps at 25°C. For purposes of this invention, viscosity is measured with a Brookfield LVTDV-11 viscometer apparatus using an RV #2 spindle at 12 rpm.
  • compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides improves the cleaning of greasy soils for various compositions, i.e., compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides. This is especially true when the compositions are used in softened water that contains few divalent ions. It is believed that calcium and/or magnesium ions increase the packing of the surfactants at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning.
  • compositions of the invention herein containing magnesium and/or calcium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
  • These ions can be present in the compositions herein at an active level of from about 0.1% to 4%, preferably from about 0.3% to 3.5%, more preferably from about 0.5% to 1%, by weight.
  • the magnesium or calcium ions are added as a hydroxide, chloride, acetate, formate, oxide or nitrate salt to the compositions of the present invention.
  • Calcium ions may also be added as salts of the hydrotrope.
  • compositions of the invention will be dependent upon the amount of total surfactant present therein.
  • the molar ratio of calcium ions to total anionic surfactant should be from about 0.25:1 to about 2:1.
  • Formulating such divalent ion-containing compositions in alkaline pH matrices may be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions.
  • divalent ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH or divalent ions alone.
  • the stability of these compositions becomes poor due to the formation of hydroxide precipitates. Therefore, chelating agents discussed hereinafter may also be necessary.
  • Detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco- amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, Hpoxygenases, ligninases, puUulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase.
  • compositions of this invention can also optionally contain from about 0.0001% to about 5%, more preferably from about 0.003% to about 4%, most preferably from about 0.005% to about 3%, by weight, of active protease, i.e., proteolytic, enzyme.
  • Protease activity may be expressed in Anson units (AU.) per kilogram of detergent composition.
  • Levels of from 0.01 to about 150, preferably from about 0.05 to about 80, most preferably from about 0.1 to about 40 AU. per kilogram have been found to be acceptable in compositions of the present invention.
  • proteolytic enzymes can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.
  • the proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-type proteases. Preferred for use herein are subtilisin-type proteolytic enzymes. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and or Bacillus licheniformis.
  • Suitable proteolytic enzymes include Novo Industri A/S Alcalase® (preferred), Esperase®, Savinase® (Copenhagen, Denmark), Gist-brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN'(preferred), which are commercially available.
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European Patent EP-B-251,446, granted December 28, 1994 and published January 7, 1988 (particularly pages 17, 24 and 98) and which are also called herein "Protease B".
  • Protease A a modified bacterial serine proteolytic enzyme
  • BPN' modified bacterial serine proteolytic enzyme
  • Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156.
  • proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • lipase and/or amylase may be also added to the compositions of the present invention for additional cleaning benefits.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases such as Ml Lipase® and Lipomax® (Gist-Brocades).
  • Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • D native lipase ex Humicola lanuginosa aspartic acid
  • L Leucine
  • the substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter).
  • Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylase Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Amylase enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylase enzymes also include those described in WO95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056.
  • Other specific amylase enzymes for use in the detergent compositions of the present invention therefore include :
  • ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO95/26397.
  • ⁇ -amylases according (a) comprising the amino sequence shown in the SEQ ID listings in the above cited reference, or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown in the SEQ ID listing.
  • ⁇ -amylases according (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn- Asp.
  • a polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%
  • ⁇ -amylases according (a-c) wherein the ⁇ -amylase is obtainable from an alkalophilic Bacillus species; and in particular, from any of the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.
  • Variants of the following parent ⁇ -amylases which (i) have one of the amino acid sequences shown in corresponding respectively to those ⁇ -amylases in (a-e), or (ii) displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said amino acid sequence; in which variants :
  • At least one amino acid residue of said parent ⁇ -amylase has been replaced by a different amino acid residue
  • At least one amino acid residue has been inserted relative to said parent ⁇ -amylase; the variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase : increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ - amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -amylase variant to the pH of the medium.
  • amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability e.g., oxidative stability, is known. See. for example J. Biological Chem., Vol. 260, No. 1 1, June 1985, pp. 6518-6521.
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases. especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability- enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb.
  • particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®.
  • Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • the preferred compositions herein may additionally comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the protease or other enzymes used in the compositions herein.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof such as are described in U.S.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p- bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • chlorine bleach or oxygen bleach scavengers can be added to compositions of the present invention to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbonate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • antioxidants like carbonate, ascorbate, etc.
  • organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • detergency builders can also be present in the compositions herein in amounts of from 0% to about 50%, preferably from about 2% to about 30%, most preferably from about 5% to about 15%. It is typical in light-duty liquid or gel dishwashing detergent compositions to have no detergent builder present.
  • compositions containing magnesium or calcium ions may require the additional presence of low levels of, preferably from 0 to about 10%, more preferably from about 0.5% to about 3%, chelating agents selected from the group consisting of bicine/bis(2- ethanol)blycine), citrate N-(2-hydroxylethyl) iminodiacetic acid (HIDA), N-(2,3- dihydroxy- propyl) diethanolamine, 1 ,2-diamino-2-propanol N,N'-tetramethyl-l,3- diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (a.k.a. bicine), and N-tris (hydroxymethyl)methyl glycine (a.k.a. tricine) are also preferred. Mixtures of any of the above are acceptable.
  • the dishwashing compositions of the present invention will generally provide a 10% aqueous solution pH of from about 4 to 11. More preferably, the compositions herein will be alkaline in nature with a 10% aqueous solution pH of from about 7 to 10.5.
  • Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. If a composition with a pH greater than 7 is to be more effective, it should contain a buffering agent capable of providing a generally more alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition.
  • the pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
  • the pKa of the buffering agent should be from about 7 to about 9.5. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
  • the buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH.
  • Preferred buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine.
  • Useful inorganic buffers/alkalinity sources include the alkali metal carbonates, e.g., sodium carbonate.
  • the buffering agent if used, is present in the compositions of the invention herein at a level of from about 0.1% to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight of the composition.
  • An especially preferred buffering agent are the class of materials known as organic diamines.
  • Preferred organic diamines are those in which pKl and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75.
  • Other preferred materials are the primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.
  • pKl and pK2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from “Critical Stability Constants: Volume 2, Amines” by Smith and Mattel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diamines.
  • the pKa of the diamines is specified in an all- aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.
  • the pKa is an equilibrium constant which can change with temperature and ionic strength; thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions.
  • the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines”.
  • the diamines useful herein can be defined by the following structure:
  • the organic diamines When tested as approximately equimolar replacements for Ca/Mg in the near neutral pH range (7-8), the organic diamines provided only parity grease cleaning performance to Ca/Mg. This achievement is not possible through the use of Ca Mg or through the use of organic diamines below pH 8 or through the use of organic diamine diacid salts below pH 8.
  • the diamines used herein are pure or free of impurities.
  • pure is meant that the diamines are over 97% pure, i.e., preferably 98%, more preferably 99%, still more preferably 99.5%, free of impurities.
  • impurities which may be present in commercially supplied diamines include 2-Methyl-l,3-diaminobutane and alkylhydropyrimidine. Further it is believed that the diamines should be free of oxidation reactants to avoid diamine degradation and ammonia formation. Additionally, if amine oxide and/or other surfactants are present, the amine oxide or surfactant should be hydrogen peroxide-free. The preferred level of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm. Amine impurities in amine oxide and betaines, if present, should be minimized to the levels referred above for hydrogen peroxide. The compositions herein may additionally contain anti-oxidants to prevent ammonium formation upon aging due to oxygen uptake from air followed by diamine oxidation.
  • the liquid or gel dishwashing detergent compositions herein may be prepared by combining the essential and optional ingredients together in any convenient order using suitable agitation to form a homogeneous product. Preferred methods for making detergent compositions of the type disclosed herein, and for preparing various components of such compositions, are described in greater detail in Ofosu-Asante: U.S. 5,474,710: Issued December 12, 1995. Due in large part to the chemical properties of the mid-chain branched surfactants of the present invention, the liquid detergent compositions defined herein are in one phase at temperatures greater than about 10°C, and during use can be diluted with water having a hardness of at least about 40 gpg with little or no degradation of performance.
  • Soiled dishes can be contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the detergent composition of the present invention.
  • the actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredient in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
  • the particular product formulation in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product.
  • a liquid detergent composition in a typical U.S. application, from about 3 ml. to about 15 ml., preferably from about 5 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml.
  • the detergent composition has a surfactant mixture concentration of from about 21% to about 44% by weight, preferably from about 25% to about 40% by weight.
  • the soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
  • the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • a liquid detergent composition in a typical European market application, from about 3 ml. to about 15 ml., preferably from about 3 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20.000 ml., more typically from about 10,000 ml. to about 15,000 ml.
  • the detergent composition has a surfactant mixture concentration of from about 20% to about 50% by weight, preferably from about 30% to about 40%, by weight.
  • the soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
  • the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • a detergent composition in a typical Latin American market application, from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl having a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 2,000 ml.
  • the detergent composition has a surfactant mixture concentration of from about 5% to about 40% by weight, preferably from about 10% to about 30% by weight.
  • the soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article.
  • the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • Another dishwashing method used worldwide involves direct application of the detergent compositions herein, either neat or diluted in a dispenser bottle, onto the soiled dishes to be cleaned. This can be accomplished by using a device for absorbing liquid dishwashing detergent, such as a sponge or dishrag, which is placed directly into a separate quantity of undiluted or somewhat diluted liquid dishwashing composition for a period of time typically ranging from about 1 to about 5 seconds.
  • the absorbing device, and consequently the undiluted or somewhat diluted liquid dishwashing composition can then be contacted individually with the surface of each of the soiled dishes to remove food soil.
  • the absorbing device is typically contacted with each dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
  • the contacting of the absorbing device with the dish surface is preferably accompanied by concurrent scrubbing. Prior to contact and scrubbing, this method may involve immersing the soiled dishes into a water bath without any liquid dishwashing detergent. After scrubbing, the dish can be rinsed under running water.
  • 6-bromo-l-hexanol 500g, 2.76 mol
  • triphenylphosphine 768g, 2.9mol
  • acetonitrile 1800 ml
  • the reaction mixture is heated to reflux for 72 hrs.
  • the reaction mixture is cooled to room temperature and transferred into a 5L beaker.
  • the product is recrystallized from anhydrous ethyl ether (1.5L) at 10°C. Vacuum filtration followed by washing with ethyl ether and drying in a vacuum oven at 50°C for 2 hrs. gives 1140g of the desired product as white crystals.
  • the water phase is washed with hexanes (500ml) and the organic phase is separated and combined with the oil phase from the water wash.
  • the organic mixture is then extracted with water 3 times (500ml each) followed by vacuum distillation to collect the clear, oily product (1 lOg) at HOC and 1mm Hg.
  • the alcohol from the preceding step Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, mechanical stirrer, and a y-tube fitted with a thermometer and a gas outlet is added the alcohol from the preceding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140 ° C. With vigorous stirring, ethylene oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight (equal to two equivalents of ethylene oxide) has been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool.
  • the desired 7-methyltridecyl ethoxylate (average of 2 ethoxylates per molecule) product is then collected.
  • the 7- methyl tridecyl ethoxylate is blended with n-tetradecanol ethoxylate (E2) to yield a composition containing at least 25% linear alcohol.
  • chloroform Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, dropping funnel, thermometer, mechanical stirring and nitrogen outlet is added chloroform and the blend of 7-methyltridecyl ethoxylate (E2) and n-tetradecanol ethoxylate (E2) from the preceding step. Chlorosulfonic acid is slowly added to the stirred mixture while maintaining 25-30°C temperature with an ice bath. Once HCl evolution has stopped slowly add sodium methoxide (25% in methanol) while keeping temperature at 25-30°C until a aliquot at 5% concentration in water maintains a pH of 10.5. To the mixture is added hot ethanol (55°C) and vacuum filtered immediately.
  • the filtrate is concentrated to a slurry on a rotary evaporator, cooled and then poured into ethyl ether.
  • the mixture is chilled to 5°C and vacuum filtered to provide the desired blend of 7-methyltridecyl / n- tetradecyl ethoxylate (average of 2 ethoxylates per molecule) sulfate, sodium salt, product.
  • Sodium alkyl sulfates, alcohol ethoxylates and sodium alkyl ethoxy sulfates were synthesized from both the C 12, 13 and C 14, 15 alcohols.
  • the acidic reaction mixture is slowly poured into a vigorously stirred beaker of 25% sodium methoxide (285.1 g , 1.32 mol) and methanol (600ml) that is cooled in an ice water bath. After pH >12 is confirmed the solution is allowed to stir about 30 minutes then poured into a stainless pan. Most of the solvent is allowed to evaporate overnight in the fume hood. The next morning the sample is transferred to a glass dish and placed in a vacuum drying oven. The sample is allowed to dry all day and overnight at 40-60°C with 25-30 inches Hg vacuum. After bottling 32 lg of yellow tacky solid, the cat SO3 analysis shows the sample is about 93% active. The pH of the sample is about 9.5.
  • the vacuum in increased to 25-30 inches Hg and maintained for an additional 45 minutes.
  • the acidic reaction mixture is slowly poured into a vigorously stirred beaker of 25% sodium methoxide (190.1 g , 0.88 mol) and methanol (400ml) that is cooled in an ice water bath. After pH >12 is confirmed the solution is allowed to stir about 30 minutes then poured into a stainless pan. Most of the solvent is allowed to evaporate overnight in the fume hood. The next morning the sample is transferred to a glass dish and placed in a vacuum drying oven. The sample is allowed to dry all day and overnight at 40-60°C with 25-30 inches Hg vacuum. After bottling 304 g of yellow tacky solid, the cat SO3 analysis shows the sample is about 95% active. The pH of the sample is about 10.1.
  • the acidic reaction mixture is slowly poured into a vigorously stirred beaker of 25% sodium methoxide (95.0 g , 0.44 mol) and methanol (300ml) that is cooled in an ice water bath. After pH >12 is confirmed the solution is allowed to stir about 30 minutes then poured into a stainless pan. Most of the solvent is allowed to evaporate overnight in the fume hood. The next morning the sample is transferred to a glass dish and placed in a vacuum drying oven. The sample is allowed to dry all day and overnight at 40-60°C with 25-30 inches Hg vacuum. After bottling 108g of yellow tacky solid, the cat SO3 analysis shows the sample is about 89% active. The pH of the sample is about 9.8.
  • Sasol C14,15 Alcohol (218.0 g , 1.0 mol).
  • the alcohol is sparged with nitrogen for about 30 minutes at 60-80°C.
  • sodium metal (1.2 g , 0.05 mol) is added as the catalyst and allowed to melt with stirring at 120-140°C.
  • ethylene oxide gas (110.0 g , 2.5 mol) is added in 140 minutes while keeping the reaction temperature 120-140°C.
  • the acidic reaction mixture is slowly poured into a vigorously stirred beaker of 25% sodium methoxide (51.8 g , 0.24 mol) and methanol (300ml) that is cooled in an ice water bath. After pH >12 is confirmed the solution is allowed to stir about 30 minutes then poured into a stainless pan. Most of the solvent is allowed to evaporate overnight in the fume hood. The next morning the sample is transferred to a glass dish and placed in a vacuum drying oven. The sample is allowed to dry all day and overnight at 40-60°C with 25-30 inches Hg vacuum. After bottling 94 g of yellow tacky solid, the cat SO3 analysis shows the sample is about 91% active. The pH of the sample is about 10.3.
  • Light-duty liquid dishwashing detergent compositions comprising the mid-chain branched surfactants of the present claims are prepared:
  • the diamine is selected from: dimethyl aminopropyl amine; 1,6-hexane diamine; 1,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3-pentanediamine; 1-methyl- diaminopropane.
  • the amylase is selected from: Termamyl®, Fungamyl®; Duramyl®; and BAN®.
  • the lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®' D96L - lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826; and the Humicola lanuginosa strain DSM 4106.
  • the protease is selected from: Savinase®; Maxatase® ; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®-
  • Hydrotropes are selected from sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.
  • DTPA is diethylenetriaminepentaacetate chelant.
  • the diamine is selected from: dimethyl aminopropyl amine; 1,6-hexane diamine; 1,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3-Pentanediamine; 1-methyl- diaminopropane.
  • the amylase is selected from: Termamyl®, Fungamyl®; Duramyl®; and BAN®.
  • the lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®' D96L - lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826; and the Humicola lanuginosa strain DSM 4106.
  • the protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®-
  • Hydrotropes are selected from sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.
  • DTPA is diethylenetriaminepentaacetate chelant.
  • the diamine is selected from: dimethyl aminopropyl amine; 1,6-hexane diamine; 1,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3-Pentanediamine; 1-methyl- diaminopropane.
  • the amylase is selected from: Termamyl®, Fungamyl®; Duramyl®; and BAN®.
  • the lipase is selected from: Amano-P; Ml Lipase®; Lipomax®; Lipolase®' D96L - lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826; and the Humicola lanuginosa strain DSM 4106.
  • the protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®-
  • Hydrotropes are selected from sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.
  • DTPA is diethylenetriaminepentaacetate chelant.

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

Abstract

L'invention concerne des compositions détergentes légères liquides ou en gel qui sont particulièrement utiles pour laver à la main de la vaisselle trés sale, dans des conditions de faible température et forte dureté. Ces compositions contiennent une solution de tensioactifs qui comprend un agent tensioactif ramifié à chaîne moyenne. En outre, ces compositions comprennent un composant tensio-actif à base d'amide d'acide gras de polyhydroxy, une quantité détergente de magnésium ou de calcium, un économiseur d'eau qui est, de préférence, un oxyde d'amine et un vecteur liquide aqueux. Les compositions détergentes présentent une excellente stabilité de phase à de faibles températures, et d'excellents taux de mélange avec de l'eau, même à de faibles températures et avec une forte dureté d'eau.
PCT/IB1998/001538 1997-10-14 1998-10-05 Compositions detergentes legeres liquides ou en gel pour laver la vaisselle comprenant des tensio-actifs ramifies a chaine mediane WO1999019439A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000515997A JP2001520264A (ja) 1997-10-14 1998-10-05 中鎖分枝鎖界面活性剤を包含する軽質液体またはゲル食器洗浄用洗剤組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6191797P 1997-10-14 1997-10-14
US60/061,917 1997-10-14

Publications (1)

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WO1999019439A1 true WO1999019439A1 (fr) 1999-04-22

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JP (1) JP2001520264A (fr)
AR (1) AR013013A1 (fr)
WO (1) WO1999019439A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002034558A (ja) * 2000-07-21 2002-02-05 Nof Corp 安定化された蛋白質分解酵素およびその用途
US6384010B1 (en) 2000-06-15 2002-05-07 S.C. Johnson & Son, Inc. All purpose cleaner with low organic solvent content
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
EP2264136A1 (fr) * 2009-06-19 2010-12-22 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
US8901058B2 (en) 2009-06-19 2014-12-02 The Procter & Gamble Company Liquid hand dishwashing detergent composition
US9267097B2 (en) 2007-02-15 2016-02-23 Ecolab Usa Inc. Fast dissolving solid detergent
CN110123224A (zh) * 2018-02-02 2019-08-16 青岛海尔洗碗机有限公司 一种洗碗机的控制方法及洗碗机
US11879111B2 (en) 2020-03-27 2024-01-23 Ecolab Usa Inc. Detergent compositions, cleaning systems and methods of cleaning cosmetic and other soils

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999019440A1 (fr) * 1997-10-14 1999-04-22 The Procter & Gamble Company Compositions de detergent pour laver la vaisselle, sous forme de gel ou de liquide, comprenant des tensioactifs ramifies en milieu de chaine
JP5283251B2 (ja) * 2006-12-01 2013-09-04 ライオン株式会社 液体洗浄剤組成物
JP6472984B2 (ja) * 2014-11-12 2019-02-20 花王株式会社 手洗い用食器洗浄剤組成物

Citations (3)

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EP0232092A2 (fr) * 1986-01-28 1987-08-12 Robert Goldman Compositions et procédés pour l'enlèvement de ternissure d'articles ménagers
WO1997038956A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Procede de fabrication d'agents tensioactifs contenant des groupes alkyles a chaine ramifiee
WO1998028393A1 (fr) * 1996-12-20 1998-07-02 The Procter & Gamble Company Compositions detergentes pour vaisselle, contenant des diamines organiques

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EP0232092A2 (fr) * 1986-01-28 1987-08-12 Robert Goldman Compositions et procédés pour l'enlèvement de ternissure d'articles ménagers
WO1997038956A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Procede de fabrication d'agents tensioactifs contenant des groupes alkyles a chaine ramifiee
WO1998028393A1 (fr) * 1996-12-20 1998-07-02 The Procter & Gamble Company Compositions detergentes pour vaisselle, contenant des diamines organiques

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Title
VARADARAJ R ET AL: "RELATIONSHIP BETWEEN FUNDAMENTAL INTERFACIAL PROPERTIES AND FOAMING IN LINEAR AND BRANCED SULFATE, ETHOXYSULFATE, AND ETHOXYLATE SURFACTANTS", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 140, no. 1, November 1990 (1990-11-01), pages 31 - 34, XP002036586 *

Cited By (17)

* 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
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
US6384010B1 (en) 2000-06-15 2002-05-07 S.C. Johnson & Son, Inc. All purpose cleaner with low organic solvent content
JP2002034558A (ja) * 2000-07-21 2002-02-05 Nof Corp 安定化された蛋白質分解酵素およびその用途
US10577565B2 (en) 2007-02-15 2020-03-03 Ecolab Usa Inc. Fast dissolving solid detergent
US9267097B2 (en) 2007-02-15 2016-02-23 Ecolab Usa Inc. Fast dissolving solid detergent
US10005986B2 (en) 2007-02-15 2018-06-26 Ecolab Usa Inc. Fast dissolving solid detergent
US11261406B2 (en) 2007-02-15 2022-03-01 Ecolab Usa Inc. Fast dissolving solid detergent
WO2010147916A1 (fr) * 2009-06-19 2010-12-23 The Procter & Gamble Company Composition liquide de détergent pour laver la vaisselle à la main
US8901059B2 (en) 2009-06-19 2014-12-02 The Procter & Gamble Company Liquid hand dishwashing detergent composition
US8901058B2 (en) 2009-06-19 2014-12-02 The Procter & Gamble Company Liquid hand dishwashing detergent composition
EP2264136A1 (fr) * 2009-06-19 2010-12-22 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
EP2264138B2 (fr) † 2009-06-19 2023-03-08 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
CN110123224A (zh) * 2018-02-02 2019-08-16 青岛海尔洗碗机有限公司 一种洗碗机的控制方法及洗碗机
US11879111B2 (en) 2020-03-27 2024-01-23 Ecolab Usa Inc. Detergent compositions, cleaning systems and methods of cleaning cosmetic and other soils
US12203050B2 (en) 2020-03-27 2025-01-21 Ecolab Usa Inc. Detergent compositions, cleaning systems and methods of cleaning cosmetic and other soils

Also Published As

Publication number Publication date
AR013013A1 (es) 2000-11-22
JP2001520264A (ja) 2001-10-30

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