EP0085448B1 - Detergenszusammensetzungen - Google Patents

Detergenszusammensetzungen Download PDF

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Publication number
EP0085448B1
EP0085448B1 EP19830200064 EP83200064A EP0085448B1 EP 0085448 B1 EP0085448 B1 EP 0085448B1 EP 19830200064 EP19830200064 EP 19830200064 EP 83200064 A EP83200064 A EP 83200064A EP 0085448 B1 EP0085448 B1 EP 0085448B1
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Prior art keywords
surfactant
alkyl
carbon atoms
composition according
weight
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EP0085448A1 (de
EP0085448B2 (de
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Brian Garston
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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

Definitions

  • This invention relates to detergent compositions.
  • it relates to detergent compositions suitable for washing fabrics, clothes etc in automatic washing machines with improved cleaning performance.
  • Cationic surfactants have been frequently incorporated into detergent compositions of various types. However, the inclusion of such cationic surfactants is generally for the purpose of providing some adjunct fabric care benefit, and not for the purpose of cleaning. For example, certain cationic surfactants have been included in detergent compositions for the purpose of yielding a germicidal or sanitization benefit to washed surfaces, as is disclosed in U.S. Patent 2,742,434, Kopp, issued April 17, 1956; U.S. Patent 3,539,520, Cantor et al, issued November 10, 1970; and U.S. Patent 3,965,026, Lancz, issued June 22 1976.
  • cationic surfactants such as ditallowdimethylammonium chloride, have been included in detergent compositions for the purpose of yielding a fabric-softening benefit, as disclosed in U.S. Patent 3,607,763, Salmon et al, issued September 21 1971; and U.S. Patent 3,644,203, Lamberti et al, issued February 22 1972.
  • Such components are also disclosed as being included in detergent compositions for the purpose of controlling static, as well as softening laundered fabrics, in U.S. Patent 3,951,879, Wixon, issued April 20 1976; and U.S. Patent 3,959,157 Inamorato, issued May 25 1976.
  • Certain water-soluble cationic surfactants are also known to enhance cleaning performance, especially on greasy and oily soils, when used in combination with nonionic or anionic surfactants, see for instance European Patent Application, Publication No. 225.
  • these compositions require relatively high levels of the cationic and nonionic surfactant components in relation to the anionic surfactant level and this can result in a lack of "robustness", particularly in the areas of clay soil detergency and whiteness maintenance, when the compositions are used in multicycle wash-wear treatments in the presence of rinse-added cationic fabric softener.
  • the compositions have their greatest effectiveness at medium to high wash temperature (50°C and above); at low wash temperatures (up to about 40°C) on the other hand, the rate of oil removal is greatly reduced and excessively long wash times are required for optimum performance.
  • the invention thus provides granular and liquid detergent compositions suitable for heavy duty laundering purposes having improved cleaning performance especially on greasy, oily and lipid soils without detriment to detergency performance on clay soils and without detriment to the soil suspending or fabric whitening characteristics of the compositions, across the range of wash temperatures and under realistic soil, fabric load and multi wash-rinse-wear cycle conditions.
  • a detergent composition having a pH in 1 % by weight aqueous dispersion of at least 7 comprising:
  • Detergent compositions of the invention contain a primary surfactant which is an anionic surfactant or a mixture thereof with nonionic, zwitterionic or ampholytic surfactants, and a cosurfactant which is a mixture of water-soluble quaternary ammonium surfactant and amine-oxide.
  • the primary surfactant constitutes from 2% to 60% of the detergent compositions, preferably from about 4% to about 25%, especially from about 8% to about 20% in the case of granular detergent composition, and preferably from about 10% to about 50%, especially from about 15% to about 40% in the case of liquid detergent compositions.
  • the auxiliary surfactant system is preferably from about 1 % to about 4% of the detergent composition with the amine oxide and quaternary ammonium surfactants being present at a weight ratio of from about 3:1 to about 1:3, with the individual cosurfactants each preferably constituting up to about 1.5% by weight of composition.
  • the weight ratio of surfactant:cosurfactant is at least 1:1, preferably from about 2:1 to about 50:1, more preferably from about 3:1 to about 20:1.
  • the anionic surfactant component is present at an equivalent ratio with respect to the water-soluble quaternary ammonium surfactant of at least 1:1. This is necessary for ensuring optimum grease and lipid soil removal and good suspension of soil in the detergent wash liquor, and for achieving excellent whiteness under multicycle wash-rinse-wear conditions.
  • compositions contain as the primary surfactant a mixture of anionic and alkoxylated nonionic surfactants in a weight ratio of from about 20:1 to about 1:5, more preferably from about 6:1 to about 1:3, especially from about 5:1 to about 1:1.
  • Such compositions are desirable from the point of view of providing optimum grease, lipid and particulate detergency.
  • Optimum performance also depends sensitively on the choice of nonionic surfactant and especially desirable from the viewpoint of grease detergency are biodegradable nonionic surfactants having a lower consolute temperature in the range from about 25°C to about 65°C, more preferably from about 30°C to about 50°C.
  • biodegradable nonionic surfactants of this type have the general formula RO(CH2CH20)nH wherein R is primary or secondary branched or unbranched 6 9 - 15 alkyl or alkenyl and n (the average degree of ethoxylation) is from 2 to 9, especially from 3 to 8.
  • More hydrophilic nonionic detergents can be employed for providing particulate detergency and anti-redeposition, however, for instance, nonionic detergents of the general formula given above wherein R is primary or secondary, branched or unbranched C S - 24 alkyl or alkenyl and n is from 10 to 40. Combinations of the two classes of nonionic surfactants can also be used with advantage of course.
  • compositions of the invention are formulated to have a pH of at least 7 in the laundry solution at conventional usage concentrations (about 1% by weight) in order to optimize cleaning performance.
  • Granular compositions herein preferably have a pH of from about 8.5 to about 11; liquid compositions preferably have a pH of from about 7.5 to about 10.5.
  • the anionic surfactant may be any one or more of the materials used conventionally in laundry detergents.
  • Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpho-carboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy alkane-1-sulphonate, and beta-alkyloxy alkane sulphonate.
  • a particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester group.
  • alkyl is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C 8-18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • anionic detergent compounds herein include the sodium C 10 - 18 alkyl glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphonates and sulphates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts or esters of a-sulphonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulphonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulphates containing from about 10 to 18, especially about 12 to 16, carbon atoms in the alkyl group and from about 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing from about 12 to 24, preferably about 14 to 16, carbon atoms, especially those made by reaction with sulphur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24, preferably from about 10 to about 22 and especially from about 16 to about 22 carbon atoms in the alkyl chain.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, from oil, soybean oil, caster oil, tallow, whale and fish oils, grease, lard and mixtures thereof).
  • the fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Napthenic acids are also suitable.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
  • Nonionic surfactants which may be used in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include:
  • the molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800.
  • Such synthetic nonionic detergents are available on the market under the Trade Name of "Pluronic” supplied by Wyandotte Chemicals Corporation.
  • Especially preferred nonionic surfactants for use herein are the C 9 ⁇ C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 12 ⁇ C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
  • a further essential component of the present compositions is an amine-oxide having the general formula I wherein R is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, each R 1 is independently selected from C 1-4 alkyl and ⁇ (C n H 2n O) m H where i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C n H 2n O groups in a molecule being no more than 7.
  • R has from 10 to 14 carbon atoms and each R' is independently selected from methyl and ⁇ (C n H 2n O) m H wherein m is from 1 to 3 and the sum total of C n H 2n O groups in a molecule is no more than 5, preferably no more than 3.
  • j is 0 and each R' is methyl, and R is C 12 ⁇ C 14 alkyl.
  • Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents.
  • a specific example of this preferred class of bis-amine oxides is: N-hydrogenated C 16 ⁇ C 18 tallow alkyl-N,N',N'tri-(2-hydroxyethyl)-propylene-1,3-diamine oxide.
  • the quaternary ammonium surfactant component of the present composition is defined by the general formula: wherein R 2 is a linear or branched alkyl, alkenyl or alkaryl group having 8 to 16 carbon atoms and each R 3 is independently selected from C 1-4 alkyl, C 1-4 alkaryl and ⁇ (C n H 2n O) m wherein i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C n H 2n O groups in a molecule being no more than 7, and wherein Z represents counter anion in number to give electrical neutrality,
  • R 2 has from 10 to 14 carbon atoms and each R 3 is independently selected from methyl and (C n H 2n O) m H wherein m is from 1 to 3 and the sum total of C n H 2n O groups in a molecule is no more than 5, preferably no more than 3.
  • j is 0, R 3 is selected from methyl, hydroxyethyl and hydroxypropyl and R is C12-C14 alkyl.
  • Particularly preferred surfactants of this class include C 12 alkyl trimethylammonium salts, C 14 alkyltrimethylammonium salts, coconutalkyltrimethyl- ammonium salts, coconutalkyldimethylhydroxyethylammonium salts, coconutalkyldimethyl- hydroxypropylammonium salts, and C 12 alkyldihydroxyethylmethylammonium salts.
  • Another group of useful cationic compounds are the diammonium salts of formula II in which j is 1, R 2 is C 12 ⁇ C 14 alkyl, each R 3 is methyl, hydroxyethyl or hydroxypropyl and i is 2 or 3.
  • R 2 is coconut alkyl
  • R 3 is methyl
  • i is 3.
  • compositions of the invention can also include at least one detergent organic or inorganic builder salt which can be any one of the water soluble or water insoluble salts conventionally used for this purpose.
  • Suitable inorganic builder salts include orthophosphates, pyrophosphates, tripolyphosphates and the higher polymeric glassy phosphates, silicates, carbonates, and the water insoluble crystalline aluminosilicates such as hydrated Zeolite A, X or P.
  • Organic builder salts include the aminocarboxylates such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetra acetic acid (EDTA) and diethylenetriaminepenta acetic acid (DETPA) and the methylene phosphonate analogues of these materials NTMP, EDTMP and DETPMP, as well as the salts of polycarboxylic acids such as lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patents 821,368, 821,369 and 821,370; succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 2-oxy-1,1,3-propane tri-carboxylic acid; oxydisuccinic acid
  • the builder salts preferably comprise from about 5% to about 70% by weight of the composition, preferably from about 10% to about 50% by weight for granular detergents, and preferably from about 5% to about 20% for liquid detergents.
  • compositions of the present invention can be supplemented by all manner of detergent components.
  • Soil suspending agents at about 0.1% to 10% by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethyl cellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invention.
  • Dyes, pigments, optical brighteners, and perfumes can be added in varying amounts as desired.
  • Enzymes suitable for use herein include those discussed in U.S. patents 3,519,570 and 3,533,139 to McCarty and McCarty et al issued July 7 1970 and January 5, 1971 respectively.
  • Anionic fluorescent brightening agents are well-known materials, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2'-disulphonate, disodium 4'4-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethyl- amino)-S-triazin-6-ylamino)stilbene-2,2'-disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2yl)stilbene-2,2'-disulphonate,
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate preferably is used in an amount from 0.5% to 10% preferably from 3% to 8%.
  • Suitable silicate solids have a molar ratio of Si0 2 /alkali metal 2 0 in the range from about 0.5 to about 4.0, but much more preferably from 1.0 to 1.8, especially about 1.6.
  • the alkali metal silicates suitable herein can be commercial preparations of the combination of silicon dioxide and alkali metal oxide, fused together in varying proportions.
  • the present compositions also contain suds regulating components in an amount of from about 0.05% to about 3%.
  • Preferred are microcrystalline waxes having a melting point in the range from 35°C-115°C and saponification value of less than 100.
  • the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
  • Suitable examples of the above waxes include microcrystalline and oxidized micro-crystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax, candelilla; and carnauba wax.
  • U.S. Patent 3,933,672 issued January 20 1976, to Bartollota et al. discloses silicone suds controlling agent suitable herein.
  • the silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
  • the silicone material can be described as siloxane having the formula: wherein x is from about 20 to 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
  • the polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agents.
  • Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenyl-, methylpolysiloxanes and the like.
  • Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 to 20 nm and a specific surface area above about 50 m 2 /g. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:10.
  • the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in DE-A-2,646,126 published April 28, 1977.
  • An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an amount from about 3% to about 40% by weight, preferably from about 8% to about 33% by weight.
  • a peroxy bleaching component for use herein include perborates persulfates, persilicates, perphosphates, percarbonates, and more generally all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions.
  • the composition can also advantageously include a bleach activator which is normally an organic compound containing an N-acyl, or an O-acyl (preferably acetyl) group.
  • Preferred materials are N,N,N',N'-tetraacetyl ethylene diamine and N,N,N',N'-tetraacetylglycouril.
  • the bleach activator is preferably added at a level from 0.5% to 5% by weight of composition.
  • a further preferred ingredient of the instant compositions is from about 0.01 to about 4%, especially from about 0.1 to about 1.0% by weight of a polyphosphonic acid or salt thereof which is found to provide bleachable stain detergency benefits.
  • Especially preferred polyphosphonates have the formula:- wherein each R is CH 2 PO 3 H 2 or a water-soluble salt thereof and n is from 0 to 2.
  • examples of compounds within this class are aminotri-(methylenephosphonic acid), ethylene diamine tetra(methylenephosphonic acid) and diethylene triamine penta(methylene phosphonic acid). Of these, ethylenediamine tetra(methylene phosphonic acid) is particularly preferred.
  • a further optional component is from about 0.1 % to about 3%, especially from about 0.25% to about 1.5% of a polymeric material having a molecular weight of from 2000 to 2,000,000 and which is a copolymer of maleic acid anhydride and a polymerisable monomer selected from C,-C '2 -alkyl vinyl ethers, acrylic and methacrylic acid and C,-C 2o esters thereof, alkenes having from 2 to 12 carbon atoms, N-vinyl pyrrolidone and styrene.
  • carboxylates are 1:1 styrene/maleic acid copolymer, di-isobutylene/maleic acid copolymers and methyl vinyl ether/maleic acid copolymers.
  • Other suitable polycarboxylates are poly-a-hydroxy acrylates and lactones thereof as described in Belgian Patent 817,678 and GB-A-1,425,307.
  • Another suitable component of the present compositions is a water soluble magnesium salt which is added at levels in the range from about 0.015% to about 0.2%, preferably from about 0.03% to about 0.15% and more preferably from about 0.05% to about 0.12% by weight of the compositions (based on weight of magnesium).
  • Suitable magnesium salts include magnesium sulfate, magnesium sulfate heptahydrate, magnesium chloride, magnesium chloride hexahydrate, magnesium fluoride and magnesium acetate.
  • the magnesium salt is added to granular compositions as part of the aqueous slurry crutcher mix and is then converted to dry granular form for instance by spray drying.
  • Liquid detergent compositions of the invention can additionally be supplemented by pH regulators such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, and mono-, di- and triethanolamine; solvents such as ethyl alcohol, isopropanol, propylene glycol, propane-1, 2-diol, hexyleneglycol; and hydrotropes such as urea.
  • pH regulators such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, and mono-, di- and triethanolamine
  • solvents such as ethyl alcohol, isopropanol, propylene glycol, propane-1, 2-diol, hexyleneglycol
  • hydrotropes such as urea.
  • Granular detergent compositions of the invention are preferably prepared by spray-drying an aqueous slurry comprising the primary surfactant, cosurfactant and detergency builder.
  • the aqueous slurry is mixed at a temperature in the range 70 ⁇ 90°C and the water-content of the slurry adjusted to a range of 25% to 45%, preferably 30%-38% by weight.
  • Spray drying is undertaken with drying gas inlet temperature of from about 250-350°C, preferably 275-330°C, providing a final moisture content in the range of from 8% to 14% by weight.
  • Nonionic surfactant, where present, can then be sprayed in fluid form onto the spray-dried detergent granules.
  • slurry is prepared containing all the components except the nonionic surfactant, silicone prill, bleach and enzyme and the slurry is then spray dried to form a granular intermediate.
  • the bleach and enzyme are then dry-mixed with the granular intermediate and the nonionic surfactant is finally sprayed onto the granular mixture. All figures are given as % by weight.
  • the above products provide excellent grease/oil and lipid soil removal performance simultaneously with good clay soil detergency and whiteness maintenance under realistic multi-cycle wash-wear conditions, including low wash temperatures and carry-over of rinse added softener.
  • the above products provide excellent grease/oil and lipid soil removal performance simultaneously with good clay soil detergency and whiteness maintenance under realistic multicycle wash-wear conditions, including low wash temperatures and carry-over of rinse added softener.

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Claims (7)

1. Detergenszusammensetzung mit einem pH-Wert von mindestens 7 in 1 gew.-%iger wäßriger Dispersion, umfassend:
(a) 2 bis 60 Gew.-% an oberflächenaktivem Mittel ausgewählt aus anionischen oberflächenaktiven Mitteln und Gemischen daraus mit nichtionischen, zwitterionischen und ampholytischen oberflächenaktiven Mitteln;
(b) 0,5 bis 6 Gew.-% an mitverwendetem oberflächenaktivem Mittel umfassend ein Gemisch mit einem Gewichtsverhältnis von 5:1 bis 1:5 aus
(i) Aminoxid mit der allgemeinen Formel I:
Figure imgb0013
worin R eine geradkettige oder verzweigtkettige Alkyl- oder Alkenylgruppe mit 8 bis 20 Kohlenstoffatomen bedeutet, jeder Rest R1 unabhängig voneinander ausgewählt ist aus C'-4 Alkylgruppen und Gruppen der Formel ―(CnH2nO)mH, wobei i eine ganze Zahl von 1 bis 6 bedeutet, j 0 oder 1 bedeutet, n 2 oder 3 bedeutet und m 1 bis 7 bedeutet, wobei die Gesamtsumme der Gruppen CnH2nO in einem Molekül nicht mehr als 7 beträgt, und
(ii) oberflächenaktiven quaternären Ammoniumverbindungen mit der allgemeinen Formel II:
Figure imgb0014
worin R2 eine geradkettige oder verzweigtkettige Alkyl-, Alkenyl- oder Alkarylgruppe mit 8 bis 16 Kohlenstoffatomen bedeutet und jeder Rest R3 unabhängig voneinander ausgewählt ist aus C'-4 Alkylgruppen, C1-4Alkarylgruppen und Gruppen der Formel―(CnH2nO)m, wobei i eine ganze Zahl von 1 bis 6 bedeutet, j 0 oder 1 bedeutet, n 2 oder 3 bedeutet und m 1 bis 7 bedeutet, wobei die Gesamtsumme der Gruppen CnH2nO in einem Molekül nicht mehr als 7 beträgt, und wobei Z ein Gegenanion in einer Anzahl, um elektrische Neutralität zu erzielen, darstellt, wobei das Gewichtsverhältnis von oberflächenaktivem Mittel zu mitverwendetem oberflächenaktivem Mittel mindestens 1:1 beträgt und wobei das Äquivalentverhältnis von anionischem oberflächenaktivem Mittel zu kationischem oberflächenaktivem Mittel ebenfalls mindestens 1:1 beträgt.
2. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß in der Formel I R 10 bis 14 Kohlenstoffatome aufweist und jeder Rest R' unabhängig voneinander ausgewählt ist aus Methylgruppen und Gruppen der Formel ―(CnH2nO)mH, worin m 1 bis 3 bedeutet und die Gesamtsumme der Gruppen CnH2nO in einem Molekül nicht mehr als 5 beträgt.
3. Zusammensetzung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß in der Formel II R2 10 bis 14 Kohlenstoffatome aufweist und jeder Rest R3 unabhängig voneinander ausgewählt ist aus Methylgruppen und Gruppen der Formel (CnH2nO)mH, worin m 1 bis 3 bedeutet und die Gesamtsumme der Gruppen CnH2nO in einem Molekül nicht mehr als 5 beträgt.
4. Zusammensetzung gemäß einem der Ansprüche 1 bis 3, gekennzeichnet durch 1 bis 4% an dem System aus mitverwendeten oberflächenaktiven Mitteln aus Aminoxid und oberflächenaktiver quaternärer Ammoniumverbindung in einem Gewichtsverhältnis von 3:1 bis 1:3.
5. Zusammensetzung gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Gewichtsverhältnis von oberflächenaktivem Mittel zu mitverwendetem oberflachenaktivem Mittel im Bereich von 2:1 bis 50:1, vorzugsweise von 3:1 bis 20:1, liegt.
6. Zusammensetzung gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das oberflächenaktive Mittel ein Gemisch aus anionischen und alkoxylierten nichtionischen oberflächenaktiven Mitteln in einem Gewichtsverhältnis von 20:1 bis 1:5, vorzugsweise von 6:1 bis 1:3, insbesondere von 5:1 bis 1:1 umfaßt.
7. Granulierte Detergenszusammensetzung gemäß einem der Ansprüche 1 bis 6, gekennzeichnet durch 4 bis 25% an oberflächenaktivem Mittel, 1 bis 4% an mitverwendetem oberflächenaktivem Mittel, 10 bis 50% an Detergensgerüststoff, 3 bis 40% an Peroxybleichmittel und 0 bis 5% an einer organischen Peroxysäure als Bleichaktivator.
EP19830200064 1982-01-25 1983-01-17 Detergenszusammensetzungen Expired EP0085448B2 (de)

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ZA856442B (en) * 1984-09-04 1987-04-29 Colgate Palmolive Co Wash cycle detergent-softener compositions having improved fabric subtanctivity
US5334503A (en) * 1991-10-08 1994-08-02 Eastman Kodak Company Test kit and method for the detection of microorganisms associated with periodontal diseases using surfactant mixture as extraction composition
WO1997012022A1 (en) * 1995-09-29 1997-04-03 The Procter & Gamble Company Stable aqueous laundry detergent compositions comprising quaternary surfactants and amine oxides and having improved suspension properties
AR003724A1 (es) * 1995-09-29 1998-09-09 Procter & Gamble Composicion detergente liquida estructurada de lavanderia, para trabajo duro, que comprende surfactantes anionicos y cationicos.
DE102010043066A1 (de) * 2010-10-28 2012-05-03 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit antimikrobieller Wirkung

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US4174304A (en) * 1975-08-01 1979-11-13 Bullen Chemical Company Midwest, Inc. Surfactant system
EP0000225A1 (de) * 1977-06-29 1979-01-10 THE PROCTER & GAMBLE COMPANY Festes Waschmittel zur verbesserten Beseitigung von fetthaltigem Schmutz
DE2967237D1 (en) * 1978-08-10 1984-10-31 Procter & Gamble Europ Liquid detergent composition containing ternary surfactant system
CH641833A5 (en) * 1978-12-18 1984-03-15 Bullen Chemical Co Midwest Inc Surface-active composition
ATE20534T1 (de) * 1981-03-07 1986-07-15 Procter & Gamble Textilbehandlungsmittel und deren zubereitung.

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