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WO1997002337A1 - Compositions detergentes liquides - Google Patents

Compositions detergentes liquides Download PDF

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Publication number
WO1997002337A1
WO1997002337A1 PCT/US1996/007447 US9607447W WO9702337A1 WO 1997002337 A1 WO1997002337 A1 WO 1997002337A1 US 9607447 W US9607447 W US 9607447W WO 9702337 A1 WO9702337 A1 WO 9702337A1
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WO
WIPO (PCT)
Prior art keywords
formula
alkyl
liquid detergent
detergent composition
cap
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PCT/US1996/007447
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English (en)
Inventor
Howard David Hutton
Phillip Kyle Vinson
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of WO1997002337A1 publication Critical patent/WO1997002337A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to liquid detergent compositions, particularly to dishwashing compositions comprising high levels of nonionic surfactants and suds enhancing polymers.
  • Non food derived soils which are often found include, for example lipstick and nicotine.
  • the soils which are the hardest to remove are usually greasy soils.
  • Particularly difficult soils to remove are those which have been baked-on or burnt-on or soils which have been allowed to harden onto the dish article.
  • Nonionic surfactants are widely used in detergent compositions. However, except for selected nonionic surfactants, the art teaches their use generally is limited to lower levels in certain polymer-containing compositions. For example, U.S. Patent 5,167,872, issued December 1 , 1992 to Pancheri et al., states: "However, when the level of anionic surfactant is less than about 20%, the compositions should not contain any substantial amount of conventional nonionic surfactant, e.g., an alkylpolyethoxylate, in addition to the polymeric surfactant. Large amounts of conventional nonionic surfactants, e.g., more than about three or four percent, tend to harm the sudsing ability of the compositions.” (At column 8, lines 25-32.)
  • Example XXIII therein provides grease control results for a composition containing a preferred polymer useful in the present invention (designated therein as compound U).
  • this composition does not contain any nonionic surfactant, consistent with the hereinbefore noted teachings of this document.
  • the present invention has discovered that selected polymers of this type provide enhanced sudsing for these liquid dishwashing compositions, even when higher than 3% nonionic surfactants are present.
  • Disclosures relating to polyhydroxy fatty acid amides include: U.S. Patent 5,332,528, to Pan et al. issued July 26, 1994; U.S. 5,288,431, to Huber et al. issued February 22, 1994; U.S. Patent 5,378,409, to Ofosu- Asante issued January 3, 1995; U.S. Patent 5,376,310, to Cripe et al. issued December 27, 1994; U.S. Patent 5,269,974, to Ofosu-Asante issued December 14, 1993; U.S.
  • the present invention is a liquid detergent composition
  • a liquid detergent composition comprising:
  • nonionic surfactants selected from alkylpolysaccharides, polyhydroxy fatty acid amides, alkyl polyethoxylates, alkyl phenol ethoxylates and mixtures thereof;
  • each Cap is independently selected from the group consisting of -CH 2 CH(SO 2 -)CH2(SO3-), -CH 2 CH(S ⁇ 3-)CH2(S ⁇ 3-), - CH 2 CH 3 , and -CH3; at least one of the E n is a poly(oxyethylene)oxy moiety having the formula -O(CH2CH2 ⁇ ) n _ ⁇ - CH2CH2O-, wherein n is from about 7 to about 43; and
  • B is a polymer backbone of the formula (T-S) m -T wherein: T is a terephthaloyl moiety having the formula -C(O)-(C6H4)-C(O)-; each S is independently selected from oxypropyleneoxy ("PG") moieties having the formulas -OCH(CH3)CH2 ⁇ - or -OCH2CH(CH3)O- and oxyethyle ⁇ eoxy (“EG”) moieties having the formula -OCH2CH2O-; m is within the range of from about 0 to about 7; and the ratio of EG:PG is less than about 3:1 , preferably less than about 1:1.
  • the present invention is a liquid detergent composition comprising one or more nonionic surfactants and selected suds enhancing polymers.
  • Nonionic Surfactants :
  • the detergent composition comprises as an essential feature at least about 3%, more preferably at least about 4%, and most preferably at least about 5% of nonionic surfactant selected from alkylpolysaccharides, polyhydroxy fatty acid amides, alkyl polyethoxylates, alkyl phenol ethoxylates and mixtures thereof.
  • nonionic surfactant selected from alkylpolysaccharides, polyhydroxy fatty acid amides, alkyl polyethoxylates, alkyl phenol ethoxylates and mixtures thereof.
  • said nonionic surfactant is selected from polyhydroxy fatty acid amides, alkyl polyethoxylates, and mixtures thereof.
  • Preferred levels are from about 3% to about 50%, more preferably from about 3% to about 30%, and most preferably from about 4% to about 20%.
  • suitable alkylpolysaccharides for use herein are nonionic alkylpolysaccharides.
  • Alkylpolysaccharides suitable for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 11 to about 30, more preferably 11 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.0 to about 10, preferably from about 1.0 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • 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.
  • 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 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.
  • the preferred alkylpolyglycosides have the formula: R2O(C n H 2n O)t(glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 0 to 3 preferably 2 to 3, t is from 0 to 10, preferably 0, x is from 1.0 to 10, preferably from 1.0 to 3, most preferably from 1.3 to 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.
  • the dishwashing compositions preferably comprise from about 0% to about 50%, more preferably from about 0.1% to about 30%, most preferably from about 0.5% to about 5% of said alkylpolysaccharide surfactant.
  • R 2 -C(O)-N(R-j)-Z wherein R-j is H, a C1.C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, preferably a C1.C4 alkyl, more preferably a C-
  • Z is preferably derived from a reducing sugar in reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose.
  • high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be utilised as well as individual sugars listed above. It should be understood that these corn syrups may yield a mixture of sugar components for Z.
  • Z is preferably selected from the group consisting of
  • nCH2OH -CH(CH 2 OH)-(CHOH)n-1-CH 2 OH, or -CH2- (CHOH)2(CHOR')(CHOH)-CH2OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 inclusive and R' is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred are the glycityls wherein n is 4, particularly CH 2 (CHOH) CH2OH.
  • Ri can be for example, N-methyl , N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R5- CO-N ⁇ can be for example cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, talloamide etc.
  • Z can be 1- deoxyglycityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • polyhydroxy fatty acid amides suitable for use herein are gemini polyhydroxy fatty acid amides having the formula:
  • X is a bridging group having from about 2 to about 200 atoms
  • Z and Z' are the same or different alcohol-containing moieties having two or more hydroxyl groups (e.g., glycerol, and units derived from reducing sugars such as glucose, maltose and the like), or either one (but not both) of Z or 71 is hydrogen
  • R and R' are the same or different hydrocarbyl moieties having from about 1 to about 21 carbon atoms and can be saturated, branched or unsaturated (e.g., oleoyl) and mixtures thereof.
  • Preferred X groups are selected from substituted or unsubstituted, branched or linear alkyl, ether alkyl, amino alkyl, or amido alkyl moieties having from about 2 to about 15 carbon atoms.
  • Preferred alkyl moieties are unsubstituted, linear alkyl moieties having the formula -(CH2)n-. wherein n is an integer from 2 to about 15, preferably from 2 to about 10, and most preferably from 2 to about 6; and also unsubstituted, branched alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3 to about 10 carbon atoms, and most preferably from 3 to about 6 carbon atoms.
  • ethylene and propylene (branched or linear) alkyl moieties are also preferred.
  • unsubstituted, branched or linear ether alkyl moieties having the formula - R2-(O-R2) m -, wherein each R is independently selected from C2-C8 branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof) and m is an integer from 1 to about 5.
  • X may also be unsubstituted, branched or linear amino and/or amido alkyl moieties having the formula -R2-(N(R 3 )-R 2 ) m -, wherein each R is independently selected from C2-C8 branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof), m is an integer from 1 to about 5, and R3 is selected from hydrogen, C-1-C5 alkyl, and -C(O)R 4 -, wherein R 4 is C1-C21 alkyl, including -C(O)R.
  • the X moiety may be derived from commercially available amine compounds such as, for example, Jeffamines ⁇ (supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 and J-D400.
  • Preferred X moieties therefore include: -(CH2)2-. -(CH2)3-, -(CH2)4-, - (CH 2 )5-, -(CH 2 )6-, -CH 2 CH(CH 3 )(CH2)3-, -(CH 2 )2-0-(CH 2 )2-, -(CH 2 ) 3 -0- (CH 2 )3-, -(CH 2 )2-0-(CH 2 )3-- -(CH 2 )2-0-(CH 2 )2-0-(CH2)2-, -(CH 2 ) 3 -0- (CH 2 )2-0-(CH 2 )3-, -(CH 2 )2-0-(CH 2 )3-O-(CH 2 )2-, -(CH 2 )2-NH-(CH 2 ) 2 -, - (CH 2 )3-NH-(CH 2 ) 3 -, -(CH 2 )2-NH-(CH 2 )3-, -(CH
  • Preferred Z and Z' groups are independently selected from polyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain with at least 2 hydroxyls (in the case of glycerol) or at least 3 hydroxyls ( in the case of other sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z and Z' preferably will be derived from a reducing sugar, more preferably Z and/or Z' is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • Z and/or Z' preferably will be selected from the group consisting of - CH 2 -(CHOH)- p -CH 2 OH, -CH(CH 2 OH)-(CHOH)p. -CH 2 OH, -CH 2 -
  • (CHOH)2(CHOR 1 )(CHOH)-CH2OH where p is an integer from 1 to 5, inclusive, and R 1 is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein p is 4, particularly - CH 2 -(CHOH)4-CH 2 OH.
  • R and R' groups are independently selected from C3-C21 hydrocarbyl moieties, preferably straight or branched chain C3-C-13 alkyl or alkenyl, more preferably straight chain C5-C-11 alkyl or alkenyl, most preferably straight chain C5-C9 alkyl or alkenyl, or mixtures thereof.
  • R-CO-N ⁇ and/or R'-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • compositions according to the present invention comprise from about 0% to about 50% , preferably from about 1% to about 20%, most preferably from about 2% to about 10%, of said poly hydroxy fatty acid amide.
  • alkyl phenol ethoxylates The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols (herein referred to as "alkyl phenol ethoxylates") are suitable for use herein. In general, 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.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein (herein referred to as "alkyl polyethoxylates").
  • alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from
  • NeodolTM 45-9 the condensation product of C14-C-15 linear alcohol with 9 moles of ethylene oxide
  • Neodol ⁇ M 23-6.5 the condensation product of C-
  • NeodolTM 45-7 the condensation product of C14-C-15 linear alcohol with 7 moles of ethylene oxide
  • NeodolTM 45.4 the condensation product of C--4-C-15 linear alcohol with 4 moles of ethylene oxide
  • TM23-3 the condensation product of C12-C-13 linear alcohol with 3 moles of ethyene oxide
  • compositions according to the present invention comprise in total from about 0% to about 50% , preferably from about 0.5% to about 10%, most preferably from about 1% to about 5%, of said alkyl phenol ethoxylates, alkyl polyethoxylates, or mixtures thereof.
  • Suds Enhancing Polymers :
  • the detergent composition also comprises as an essential feature at least about 0.1%, more preferably at least about 0.5%, and most preferably at least about 1% of one or more suds enhancing polymers having the formula:
  • each Cap is independently selected from the group consisting of -CH2CH(S ⁇ 2-)CH2(S ⁇ 3"), -CH2CH(SO3-)CH2(SO3-), - CH 2 CH 3 , and -CH3; at least one of the E n is a poly(oxyethylene)oxy moiety having the formula -O(CH2CH2 ⁇ ) n _* ⁇ - CH2CH2O-, wherein n is from about 7 to about 43; and
  • B is a polymer backbone of the formula (T-S) m -T wherein: T is a terephthaloyl moiety having the formula -C(O)-(C6H4)-C(O)-; each S is independently selected from oxypropyleneoxy ("PG") moieties having the formulas -OCH(CH3)CH2O- or -OCH2CH(CH3)O- and oxyethyleneoxy ("EG”) moieties having the formula -OCH2CH2O-; m is within the range of from about 0 to about 7; and the ratio of EG:PG is less than about 3:1 , preferably less than about 1:1.
  • a preferred polymer for use herein has the formula hereinbefore wherein:
  • Preferred levels of polymer are from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, and most preferably from about 0.5% to about 2%.
  • the detergent composition may comprise a number of optional ingredients such as additional surfactants, builders, chelants, soil release agents, anti- redeposition agents, polymeric dispersing agents, bleaches, enzymes, calcium and magnesium ions, brightener, perfumes and dyes.
  • additional surfactants such as sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium EDTA, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium
  • Suitable optional surfactants for use herein include other anionic, nonionic, cationic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • Anionic surfactants suitable for use herein may be essentially any anionic surfactant, including anionic sulphate or carboxylate surfactant.
  • suitable alkyl or hydroxyalkyl alkoxylated sulphates for use herein are of the formula RO(A) m SO3M, wherein R is an unsubstituted C-11-C24 alkyl or hydroxyalkyl component, preferably a C-12- 20 - alkyl or hydroxyalkyl, more preferably a C12-C18 alkyl or hydroxyalkyl component, A is an ethoxy or propoxy group, m is from 1 to 15, more preferably from 1 to 10, and M is H or a cation which may be selected from metal cations such as sodium, potassium, lithium, calcium, magnesium, ammonium or subsituted ammonium.
  • substituted ammonium cations include methyl-, dimethyl-, trimethyl- ammonium and quaternary ammonium cations such as tetramethyl ⁇ ammonium, dimethyl piperidium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof.
  • exemplary surfactants are C-
  • 4 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.
  • compositions may comprise from about 5% to about 50%, preferably from about 5% to about 35%, most preferably from about 10% to about 25% of said alkyl alkoxylated sulphate.
  • the detergent composition may comprise from about 5% to about 50%, preferably from about 10% to about 25% of said detersive sulphonate.
  • the anionic sulphate surfactant may be any organic sulphate surfactant.
  • the counterion for the anionic sulphate surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium, or alkanol-ammonium, and mixtures thereof, with calcium and magnesium being preferred for cleaning and sudsing respectively.
  • anionic surfactants for use herein include C9-C-17 acyl- N-(C1-C4 alkyl) glucamine sulphate.
  • Anionic alkyl ethoxy carboxylate surfactant Anionic alkyl ethoxy carboxylate surfactant
  • Alkyl ethoxy carboxylates suitable for use herein include those with the formula RO(CH2CH2 ⁇ )x CH2C00-M + wherein R is a C12 to C ⁇ Q alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20%, preferably less than 15%, most preferably less than 10%, and the amount of material where x is greater than 7, is less than 25%, preferably less than 15%, most preferably less than 10%, the average x is from 2 to 4 when the average R is C13 or less, and the average x is from 3 to 6 when the average R is greater than C-13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium mono., di-, and tri-ethanol- ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred alkyl ethoxy carboxylates
  • Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula:
  • Secondary soap surfactants (aka “alkyl carboxyl surfactants”) useful herein are those which contain a carboxyl unit connected to a secondary carbon. It is to be understood herein that the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates.
  • the secondary soap surfactants should contain no ether linkages, no ester linkages and no hydroxyl groups. There should be no nitrogen atoms in the head-group (amphiphilic portion).
  • the secondary soap surfactants usually contain 10-16 total carbon atoms, as is described for example in PCT application WO 94/12608, published June 9, 1994 by The Procter & Gamble Company.
  • a highly preferred class of secondary soaps useful herein comprises the secondary carboxyl materials of the formula R 3 CH(R 4 )COOM, wherein R 3 is CH3(CH2)x and R 4 is CH3(CH2)y, wherein y can be 0 or an integer from 1 to 6, x is an integer from 6 to 12 and the sum of (x + y) is 6-12, preferably 7-11 , most preferably 8-9.
  • Another class of secondary soaps useful herein comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R5-R6-COOM, wherein R5 is C 7 -C 1 0, preferably C ⁇ -C ⁇ , alkyl or alkenyl and R ⁇ is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R 5 can be in the ortho, meta or para position relative to the carboxyl on the ring.) C.
  • Still another class of secondary soaps comprises secondary carboxyl compounds of the formula CH3(CHR) k -(CH 2 )m-(CHR) n -CH(COOM)(CHR) 0 - (CH2)p-(CHR) q -CH3, wherein each R is C-1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.
  • the species M can be any suitable, especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri- alkanolammonium, and C1-C5 alkyl substituted ammonium.
  • Sodium is convenient, as is diethanolammonium.
  • 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, fatty oleyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, alkyl phosphates, alkyl succinates and sulphosuccinates, monoesters of sulphosuccinate (especially saturated and unsaturated C- * 2-C-
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap fatty oleyl glycerol sulphates, alkyl
  • 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).
  • compositions according to the present invention may comprise at least about 3%, preferably from about 3% to about 40%, most preferably from about 3% to about 30% of said anionic surfactants.
  • compositions may comprise from about 0% to about 30%, preferably from about 0.1% to about 25%, more preferably from about 0.5% to about 20% of said optional nonionic surfactants.
  • condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • nonionic surfactant examples include certain of the commercially available TetronicTM compounds, marketed by BASF. Amphoteric surfactant
  • Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula:
  • R is a C ⁇ -C-j ⁇ alkyl group
  • Rj is of the general formula: (CH2) x COO-M / (CH 2 ) x COO-M
  • R 1 is a (CH2) x COOM or CH2CH2OH, and x is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred R alkyl chain length is a C-
  • a preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • a suitable example of an alkyl amphodicarboxylic acid for use herein is the amphoteric surfactant Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Amine oxide surfactant
  • compositions are amine oxides, individually or as amine oxide mixtures comprising a first amine oxide according to the formula R-1 R2R3N-O, wherein R- * and R2 are independently C-1-C3 alkyl or hydroxy alkyl groups and R3 is an hydrocarbyl group having an average carbon chain length of C7-C9.
  • Said first amine oxide is in combination with a second amine oxide according to the formula R4R5R6N-O wherein R4 and R5 are independently C---C3 alkyl or hydroxyalkyl groups and RQ is a C-12- 14 hydrocarbyl group and mixtures thereof.
  • R-] , R2, R4 and R5 are methyl groups.
  • R3 is preferably an alkyl group with an average carbon chain length of 8. More preferably R3 is a linear Cs alkyl group, although it may exhibit a degree of branching.
  • the ratio of said first amine oxide to said second amine oxide is from 100:1 to 1 :100 more preferably from 50:1 to 1 :50, most preferably from 10:1 to 1 :10.
  • the present invention preferably comprises from about 0% to about 20%, preferably from about 0.5% to about 15%, more preferably from about 1 % to about 15% of an amine oxide or mixture of amine oxides.
  • an amine oxide mixture comprises from about 1% to about 99%, more preferably from about 5% to about 90% of said first amine oxide.
  • amine oxides useful as amphoteric surfactants may be used herein.
  • Such optional but highly preferred amine oxides suitable for use have the formula:
  • R7 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 10 to 20 carbon atoms, preferably 10 to 14 carbon atoms; and R8 and Rg are independently
  • _3 alkyl or C2-3 hydyroxyalkyl groups or a polyethylene oxide group containing from 1 to 3, preferably 1 , ethylene oxide groups.
  • These amine oxide surfactants in particular include C-10-C14 alkyl dimethyl amine oxides and C-
  • Zwitterionic surfactants can also be incorporated into the detergent compositions herein.
  • compositions may thus comprise betaines.
  • betaines useful, as zwitterionic surfactants, in the present invention are those compounds having the formula R(R 1 )2N + R 2 COO _ wherein R is a C ⁇ -C-j ⁇ hydrocarbyl group, preferably a C10-C16 alkyl group or C- * o-16 acylamido alkyl group, each R 1 is typically C-1-C3 alkyl, preferably methyl, and R 2 is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C1-C2 alkylene group.
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C ⁇ * 2-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4-[Ci4_-
  • Preferred betaines are C-12-I8 dimethyl-ammonio hexanoate and the C-
  • R is a hydrocarbon group having from 7 to 22 carbon atoms, preferably 12 to 14 carbon atoms
  • A is the group (C(O))
  • n is 0 or 1
  • R- * is hydrogen or a lower alkyl group
  • x is 2 or 3
  • y is an integer of 0 to 4
  • Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium and B is hydrogen or a group Q as defined.
  • the composition may comprise from 0% to 10%, preferably from 0% to 5% of said betaines.
  • the sultaines useful in the present invention are those compounds having the formula (R(R 1 )2N + R 2 SO3 " wherein R is a Ce-C-is hydrocarbyl group, preferably a C-10-C16 alkyl group, more preferably a C12-C13 alkyl group, each R 1 is typically C-1-C3 alkyl, preferably methyl, and R 2 is a C ⁇
  • R is a Ce-C-is hydrocarbyl group, preferably a C-10-C16 alkyl group, more preferably a C12-C13 alkyl group, each R 1 is typically C-1-C3 alkyl, preferably methyl, and R 2 is a C ⁇
  • compositions according to the present invention may additionally comprise enzymes.
  • Suitable enzymes for use herein include lipolytic enzymes, proteolytic enzymes and amylolytic enzymes.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes described for example in
  • Preferred commercially available proteolytic enzymes include Alcalase and Savinase (Novo Industries A/S) and Maxatase
  • amylases include for example alpha-amylases obtained from a special strain of B licheniforms, described for example in GB 1 269 839.
  • Preferred commercially available amylases include Termamyl (Novo Industries A/S).
  • the compositions according to the present invention may comprise from 0.001 % to 1% , more preferably from
  • composition may comprise an enzyme stabilising system.
  • Liquid dishwashing compositions may comprise any of the ingredients listed herein above.
  • the dishwashing compositions may comprise other ingredients such as bleaches, bactericides, anti-tarnish agents, chelants, suds enhancers, opacifiers, solvents, hydrotropes, calcium and magnesium ions and perfumes and dyes.
  • a hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0% to 40%, preferably from 1% to 15%, by weight.
  • Useful hydrotropes include sodium, potassium, calcium and ammonium salts of xylene sulphonates, toluene sulphonate and cumene sulphonate and mixtures thereof.
  • Other compounds useful as hydrotropes herein include polycarboxylates and urea. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties.
  • alkyl amphodicarboxylic acid of the generic formula: .(CH 2 ) ⁇ COO-
  • R is a Cs to C-j 8 alkyl group, x is from 1 to 2
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
  • the preferred alkyl chain length (R) is a C-
  • alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol RTM 2CM Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • compositions of the invention will most preferably contain an organic solvent system present at levels of from about 1 % to about 30% by weight, preferably from about 1% to about 20% by weight, more preferably from about 2% to about 15% by weight of the composition.
  • the organic solvent system may be a mono, or mixed solvent system; but is preferably in mixed solvent system.
  • at least the major component of the solvent system is of low volatility.
  • Suitable organic solvents for use herein has the general formula:
  • R is an alkyl, alkenyl, or alkyl aryl group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4.
  • R is an alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2.
  • R groups are n-butyl or isobutyl.
  • solvents useful herein include the water soluble CARBITOL or CELLOSOLVE solvents. These solvents are compounds of the 2-(2- alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl. Other suitable solvents are benzyl alcohol, and diols such as 2- ethyl-1 ,3-hexanediol and 2,2,4-trimethl-1 ,3-pentanediol. The low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.
  • alkane mono and diols especially the C-j-C ⁇ alkane mono and diols are suitable for use herein.
  • C-J-C4 monohydric alcohols eg: ethanol, propanol, isopropanol, butanol and mixtures thereof
  • ethanol particularly preferred.
  • compositions according to the present invention may additionally comprise thickening agents, such as polyquatemium cellulose cationic polymer, for example QuatrisoftR available from the Amerchol Corporation.
  • thickening agents such as polyquatemium cellulose cationic polymer, for example QuatrisoftR available from the Amerchol Corporation.
  • compositions according to the present invention may optionally comprise from about 0.01% to about 3%, more preferably from about 0.15% to about 0.9% of calcium ions. It has been found that the presence of calcium greatly improves the cleaning of greasy soils for compositions containing polyhydroxy fatty acid amide. This is especially true when the compositions are used in softened water, which contains few divalent ions.
  • the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, xylene sulphonate, or nitrate salt. If the anionic surfactants are in the acid form, the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.
  • the calcium ions may be present in the compositions as salts.
  • the amount of calcium ions present in compositions of the invention may be dependent upon the amount of total anionic surfactant present herein.
  • the molar ratio of calcium ions to total anionic surfactant is preferably from 1:0.1 to 1:25 more preferably from 1 :2 to 1:10, for compositions of the invention.
  • malic, maleic or acetic acid, or their salts may be added to the composition of the present invention comprising calcium .
  • malic, maleic or acetic acid, or their salts can be added at levels of from 0.05% to 10% of the composition and a molar ratio with calcium of from 10:1 to 1 :10.
  • magnesium ions are preferably added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing.
  • the magnesium can be added by neutralisation of the acid with a magnesium oxide or magnesium hydroxide slurry in water. Calcium can be treated similarly. This technique minimises the addition of chloride ions, which reduces corrosive properties.
  • the neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH. pH of the compositions
  • compositions according to the present invention formulated for use in manual dishwashing applications are preferably formulated to have a pH at 20°C of from about 3 to about 12, preferably from about 6 to about 9, most preferably from about 6.5 to about 8.5.
  • compositions may be formulated for use as in pre-treatment applications whereby the composition is applied in essentially the concentrated form onto the dishes. Preferably the composition is allowed to remain on the dishes for a period of time.
  • Compositions for use in such applications preferably have a pH of from about 3 to about 14, more preferably from about 3 to about 5 or greater than about 8.
  • the detergent compositions are liquid detergent compositions.
  • the compositions are high active formulations such that said compositions comprise 75% to 50% by weight, preferably from 70% to 55% by weight, most preferably from 65% to 55% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred monohydric alcohol or a mixture of water and C1-C4 dihydric alcohol (e.g.: propylene glycol).
  • the detergent composition may be in a concentrated form, such that the composition is diluted in water prior to usage.
  • EXAMPLES 1-2 The following liquid compositions of the present invention are prepared by mixing the listed ingredients in the given amounts.
  • C12,13E2.2Sulfate Mixed C12 and C13 alkyl ethoxy sulfate, having an average of 2.2 ethoxy units per molecule.
  • C12.14 polyhydroxy fatty acid amide Mixed C12 and C14 fatty acid N-methyl glucamide.
  • Polymer a suds enhancing polymer of formula Cap - E - B - E
  • C12.14 polyhydroxy fatty acid amide Mixed C12 and C14 fatty acid N-methyl glucamide.

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  • Wood Science & Technology (AREA)
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Abstract

Cette invention concerne des compositions détergentes liquides, et tout particulièrement des compositions détergentes de lavage de vaisselle, qui comportent des niveaux élevés de tensioactifs non ioniques et de polymères renforçateurs du pouvoir moussant représentés par la formule Cap-En-B-En-Cap.
PCT/US1996/007447 1995-06-30 1996-05-22 Compositions detergentes liquides WO1997002337A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO1997044429A1 (fr) * 1996-05-18 1997-11-27 HÜLS Aktiengesellschaft Produits de lavage et de nettoyage avec polymeres enlevant les salissures
WO1999027053A1 (fr) * 1997-11-21 1999-06-03 The Procter & Gamble Company Compositions liquides a mousse durable pour le lavage de la vaisselle
EP1005890A1 (fr) * 1998-12-02 2000-06-07 Wacker-Chemie GmbH Compositions anti-mousse à base de silicone contenant du polyester
US7335700B2 (en) 1999-05-26 2008-02-26 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants

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EP0221774A2 (fr) * 1985-10-31 1987-05-13 The Procter & Gamble Company Composition détergente liquide
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WO1992017523A1 (fr) * 1991-03-28 1992-10-15 The Procter & Gamble Company Agents antisouillure non ioniques
EP0576777A1 (fr) * 1992-06-29 1994-01-05 The Procter & Gamble Company Compositions détergentes liquides aqueuses concentrées contenant polyvinylpyrrolidone et un polymère antisalissure à base de polytéréphtalate
DE4344357A1 (de) * 1993-12-24 1995-06-29 Henkel Kgaa Flüssiges Wasch- und Reinigungsmittel

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EP0185427A2 (fr) * 1984-12-21 1986-06-25 The Procter & Gamble Company Polyesters blocs et composés similaires utiles comme agents de détachage dans les compositions de détergent
US4702857A (en) * 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
EP0221774A2 (fr) * 1985-10-31 1987-05-13 The Procter & Gamble Company Composition détergente liquide
US5167872A (en) * 1985-10-31 1992-12-01 The Procter & Gamble Company Comprising anionic surfactant polymeric nonionic surfactant and betaine surfactant
EP0357280A2 (fr) * 1988-08-26 1990-03-07 The Procter & Gamble Company Agents antisalissures ayant des groupes terminaux sulfonés dérivés de groupes allyliques
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WO1992017523A1 (fr) * 1991-03-28 1992-10-15 The Procter & Gamble Company Agents antisouillure non ioniques
EP0576777A1 (fr) * 1992-06-29 1994-01-05 The Procter & Gamble Company Compositions détergentes liquides aqueuses concentrées contenant polyvinylpyrrolidone et un polymère antisalissure à base de polytéréphtalate
DE4344357A1 (de) * 1993-12-24 1995-06-29 Henkel Kgaa Flüssiges Wasch- und Reinigungsmittel

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997044429A1 (fr) * 1996-05-18 1997-11-27 HÜLS Aktiengesellschaft Produits de lavage et de nettoyage avec polymeres enlevant les salissures
WO1999027053A1 (fr) * 1997-11-21 1999-06-03 The Procter & Gamble Company Compositions liquides a mousse durable pour le lavage de la vaisselle
US6277811B1 (en) 1997-11-21 2001-08-21 The Procter & Gamble Company Liquid dishwashing detergents having improved suds stability and duration
EP1005890A1 (fr) * 1998-12-02 2000-06-07 Wacker-Chemie GmbH Compositions anti-mousse à base de silicone contenant du polyester
US7335700B2 (en) 1999-05-26 2008-02-26 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US9044413B2 (en) 1999-05-26 2015-06-02 Solvay Usa Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants

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