EP0000225A1 - Solid detergent composition for improved greasy soil removal - Google Patents

Solid detergent composition for improved greasy soil removal Download PDF

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Publication number
EP0000225A1
EP0000225A1 EP78200050A EP78200050A EP0000225A1 EP 0000225 A1 EP0000225 A1 EP 0000225A1 EP 78200050 A EP78200050 A EP 78200050A EP 78200050 A EP78200050 A EP 78200050A EP 0000225 A1 EP0000225 A1 EP 0000225A1
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EP
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Prior art keywords
carbon atoms
anionic
alkyl
surfactant
water
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German (de)
English (en)
French (fr)
Inventor
Rory James Maxwell Smith
Allan Campbell Mcritchie
Lionel Breton
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D1/86—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
    • C11D1/02—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 improved greasy soil removal capabilities. More specifically the detergent compositions of this invention provide good detergency performance on greasy and oily soils having a marked particulate soil content.
  • 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.
  • certain catronic 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
  • Other cationic surfactants 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.
  • compositions comprising mixtures of anionic, cationic and nonionic surfactants are also known in the art.
  • compositions conferring enhanced antistatic character to textiles washed therewith are described in B.P. 873,214 while compositions having enhanced germidical and detergency performance are disclosed in B.P. 641,297.
  • a solid particulate detergent composition comprising
  • Detergent compositions of the present invention contain as an essential ingredient a three-component active system comprising anionic, alkoxylated nonionic and water-soluble cationic surfactants.
  • This active system comprises from about 2% to about 60% by weight of the compositions.
  • the active system is generally in the range from about 4% to about 30%, more preferably from about 6% to about 15% by weight of the compositions.
  • compositions of the present invention are pref- ably formulated to have a pH of at least about 6 in the laundry solution at conventional usage concentrations (about 1% by weight) in order to optimize cleaning performance. More preferably, they arc alkaline in nature when placed in the laundry solution and have a pH greater than about 7, especially greater than about 8. At the higher pH values, the surface activity of the compositions of the invention is enhanced and, in certain instances, is quite markedly enhanced.
  • the anionic and cationic surfactants have a combined total of no more than 34 carbon atoms counted in hydrophobic groups having at least 4 consecutive carbon atoms (eg. alkyl, alkaryl, aryl, alkaryl, aralkyl groups etc.). In more preferred systems the number of such hydrophobic group carbon atoms totals from about 18 to 33, especially from about 26 to 32, with the anionic surfactant providing at least 12 of the carbon atoms.
  • an essential feature of the present compositions is that the surfactant system must be substantially neutral in surfactant anions and cations or else have an ionic excess of surfactant anions over surfactant cations. This is important not only with regard to optimizing grease removal, but also for ensuring good suspension of soil in the detergent wash liquor (ie. for preventing soil redeposition) and also for ensuring that water-insoluble anionic effect agents such as anionic florescers retain their effectiveness in composition. It is, of course, well known, that anionic fluorescers are quenched or inhibited in effectiveness in the presence cf cationic surfactants. Surprisingly, the grease and oil detergency benefits of the present invention are secured without suppression of fluorescer activity. It is accordingly highly important that the overall anionic:cationic surfactant equivalent ratio in the present compositions is, within manufacturing error, at least 1:1.
  • the manufacturing in the anionic and cationic surfactant components 5% by weight for each component.
  • Subjet to the above conditions be weight ratio of anionic:cationic surfactant can vary in the range from about 5:1 to about 1:3, especially From about 2:1 to about 1:2, the weight ratio of nonionic:cationic from about 300:1 to about 2:3, especially from about 20:1 to about.1:1, and the weight ratio of anionic: nonionic from about 7:1 to about 1:20, especially from. about 2:1 to about 1:10.
  • the surfactant system preferably comprises at least about 5% by weight of the water-soluble cationic surfactant and at least about 60% by weight in total of the anionic and nonionic surfactants.
  • the surfactant system comprises at least 15% by weight of each of the anionic and cationic surfactants and from 15% to 60% by weight of the nonionic surfactant. In another preferred embodiment, the surfactant system comprises at least 5% by weight of each of the anionic and cationic surfactants-and at least 60% by weight of the nonionic surfactant.
  • the cationic surfactant component of the composition of the invention is characterised as being water-soluble.
  • water solubility we refer in this context to the solubility of cationic surfactant in monomeric form, the limit of solubility being determined by the onset of micellisation and measured in terms of critical micelle concentration (C.M.C.).
  • the cationic surfactant should thus have a C.M.C. for the pure material greater than about 200 p.p.m. and preferably greater than about 500 p.p.m., specified at 30°C and in distilled water.
  • Literature values are taken where possible, especially surface tension or conductimetric values - see Critical Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS 36, (1971).
  • the ternary active system itself must be water-dispersible or water-soluble in combination with the remainder of the detergent composition. This implies that, in an equilibrium aqueous mixture of the detergent composition(containing about 1000 p.p.m. of surfactant)the ternary active system exists in one or more liquid, (as opposed to solid) surfactant/ water phases. Expressed in another way, the surfactant
  • a further essential component of the present compositions is at least 10%, preferably from about 20% to about.70% by weight of a detergency builder, for example, a water-soluble inorganic or organic electrolyte, Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and Include the common alkaline polyvalent calcium ion sequestering agents. Water-insoluble calcium ion exchange materials can also be used with advantage, however. Surprisingly, it is found that the grease removal performance of the present compositions depends sensitively on the ionic strength and the level of free hardness ions in the detergent liquor and these parameters must be closely controlled for optimum performance.
  • the builder: surfactant weight ratio is preferably greater than about 1:3, more preferably greater than about 4:1 and especially greater than about 8:1.
  • the weight ratio of calcium ion sequestering or exchange agent:surfactant is preferably greater than about 1:1 and especially greater than about 3:1, wnile the electrolyte:surfactant weight ratio is preferably greater than about 3:1, especially greater than about 6:1.
  • Optimum grease and particulate detergency 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(CH 2 CH 2 0) n H wherein R is primary or secondary branched or unbranched C 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 unbranced C 8-24 alkyl or alkenyl and n is from 10 to 40. Combinations of the two classes of nonionic surfactants The Caltionic Surfactant
  • the caltonic surfactant is a water-soluble quaternary ammonium compound having a critical micelle concentration of at least 200 p.p.m. at 30°C
  • the preferred cationic surfactant comprises from 1 to about 4 quaternary ammonium groups of which only one has the general formula:- wherein each R 1 is a hydrophobic alkyl or alkenyl group optionally substituted or 'nterrupced by phenyl, ether, ester or amide groups totalling from 8 to 20 carbon atoms and which may additionally contain up to 20 ethoxy groups, m is a number from 1 to 3 and no more than one R 1 can have more than 16 carbon atoms when m is 2 and no more than 12 carbon atoms when m is 3, each.R 2 is an alkyl group containing from one to four carbon atom or a benzyl group with no more than one R 2 in a molecule being benzyl, and x is from 0 to 3.
  • a highly preferred group of cationic surfactants of this type have the general formula: ammonium halide and di-C 10 alkyldimethylammonium halide materials.
  • the R 1 chains should be less than 9 carbon atoms in length.
  • An example is trioctyl- methyl ammonium chloride.
  • the reason for this chain length restriction is the relative insolubility of these tri - and di-long chain materials.
  • Another group of useful cationic compounds are the polyammonium salts of the general formula: wherein R 3 is selected from C 8 to C 20 alkyl, alkenyl and alkaryl groups; each R 4 is C 1 -C 4 alkyl; n is from 1 to 6; and m is from 1 to 3.
  • a further preferred type of cationic component was the formula: wherein R 1. is C 1 to C 4 alkyl; R 2 is C 5 to C 30 straight or branched chain alkyl or alkenyl, alkyl benzene, or R 3 is C 1 to C 20 alkyl or alkenyl; a is 0 or 1; n is O or 1; m is from 1 to 5; Z 2 and Z 2 are each selected from the group consisting of: and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes-the compound water-soluble, preferably selected from the group consisting of aride, methyl sulfate, hydroxide, and nitrate preferably chloride, bromide or iodine.
  • this particular cationic component is enviromentally desirable, since it is biode-, gradable, both in terms of its long alkyl chain and its containing segment.
  • choline ester derivatives having the following formula : as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse
  • p may be from 0 to 20.
  • the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
  • the choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-halocthanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize triethanolamine, forming the desired cationic component.
  • Another type of novel particularly preferred cationic material has the formula : and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide.
  • X is an anion which will make the compound water-soluble and is selected from the group consisting of halides, methylsulfate, hydroxide and nitrate, particularly chloride, bromide and iodide.
  • surfactants when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal.
  • the detergent compositions control static nd soften the fabrics laundered therewith, and inhibit the transfer of dyes in the washing solution.
  • these novel catienic surfactants are environmentally desirable, since both their long chain alkyl segments and their nitrogen segments are biodegradable.
  • the preferred choline derivatives may be prepared by the reaction of a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride.
  • the naid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester. which is then quaternized with a methyl halide to form the desired choline ester compound.
  • Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in of heat and an acid product. is then quaternized er used to
  • Water-soluble salts of the higher fatty acids are useful as the anionic detergent component of the compositions herein.
  • This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
  • a highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term “alkyl” is the alkyl portion of acyl groups).
  • Examples of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols C 8 -C 18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in U.S.P. 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C 11.8 LAS.
  • ⁇ preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of "ethoxylation of from about 1 to 4 mols of ethylene oxide.
  • anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from callow and coconut oil; sodium coconut oil fatty acid moncglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate 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 of esters of a-sulfonated 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-sulfonic 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 sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of clefin sulfonates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from
  • Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate naving from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal preferably sodium: and from about 2% to about 15% by weight of an alkyl ethoxy sulfate saving from 10 to 20 carbon atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium.
  • the nonionic detergent materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene 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 detergents include:
  • a highly preferred mixture of surfactants is a mixture of a C 8 -C 22 alkyl benzene sulfonate and a C 9 -C 15 alkanol ethoxylated with from 3 to 8 moles of ethylene oxide per mole of alkanol.
  • Highly preferred mixtures include C 12 alkyl benzene sulfonate and C 14 -C 15 alcohol-(7)-ethoxylate, in ratios of from 2:1 to 1:10, preferably 1:1 to 1:8.
  • C 8 -C 24 alkanol ethoxylate with from 10 to 40 moles of ethylene oxide per mole of alkanol is added to the above-described mixture, preferably at a level of from 1% to 5%.
  • the Detergent composition of the invention also contains at least about 10% of a detergency builder, especially a water-soluble inorganic or organic electrolyte.
  • Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents.
  • the builder can also include water-insoluble calcium ion exchange materials, however,
  • suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, sulfates and chlorides. Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates, pyrophosphates, hexametaphosphates and sulfates.
  • suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and amino- polyacetates, for example, sodium and potassium glycinates, ethylenediamine tetraacetates, nitrilotriacetates, and N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosponates, including sodium, potassium, and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like.
  • water-soluble polycarboxylates such as tnc salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, cyclopentane-cis, cis, cis - tetracarboxylic acid, mellitic acid and pyromellitic acid; (5) water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and salts thereof.
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755.038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgium Patent 814,874, issued November 12, 1974, incorporated herein by reference.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates having the, formula wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grains/gallon/minute/gram.
  • a preferred material is
  • compositions of the present invention can be supplemented by all manner of detergent components, either by including such components in the aqueous slurry to be dried or by admixing such components with the compositions of the invention following the drying step.
  • 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, pigment 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-methylN-2-hydroxyethylamino)-s-triazin.
  • 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 SiO 2 /alkali metal 2 O in the range from about 0.6 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.
  • compositions of this invention can require the presence of a suds regulating or suppressing agent.
  • Suds regulating components are normally used in an amount from about 0.001% to about 5%, preferably from about 0.05% to about 3% and especially from about 0,10% to about 1%.
  • the suds suppressing (regulating) agents which are known to be suitable as suds suppressing agents in detergent context can be used in the compositions herein. These include the silicone suds suppressing agents, especially the mixtures of silicones and silica described in U.S. Patent No. 3,933,672, the disclosure of which is incorporated herein by reference.
  • a particularly preferred suds suppressor is the material known as "HYFAC", the sodium salt of a long-chain (C 20 -C 24 ) fatty acid.
  • Microcrystalline waxes having a melting point in the range from 35 0 C-115 0 C and saponification value of less than 100 represent an additional example of a preferred suds regulating component for use in the subject compositions.
  • 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 microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
  • 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.
  • suitable peroxy bleach components for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and more in general 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.
  • a further preferred ingredient of the instant compositions is from about 0.01 to about 4%, especially from about 0.5 to about 2.2% 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 O to 2.
  • Examples of compounds within this class are aminotri-(methylenephosphonic acid), aminotri-(ethylidenephosphonic acid), ethylene diamine tetra (methylenephosphonic acid) and diethylene triamine penta (methylene phosphonic acid). Of these, ethylene diamine tetra(methylene phosphonic acid) is particularly preferred.
  • a further optional, though preferred 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 or anhydride and a polymerisable monomer selected from compounds of formula: wherein R 1 is CH 3 or a C 2 to C 12 alkyl group; wherein R 2 is H or CH 3 and R 3 is H, or a C 1 to C 10 alkyl group; wherein each of R 4 and R 5 is H or an alkyl group such that R 4 and R 5 together have 0 to 10 carbon atoms; and (vi) mixtures of any two or more thereof, said copolymers being optionally whelly or partly neutralised at the carboxyl groups by sodium or potassium.
  • carboxylates are 1:1 styrene/maleic acid copolymer, di-isobutylene/maleic acid copolymers and methyl vinyl ether/maleic acid copolymers.
  • polycarboxylates are poly-a-hydroxy acrylic acids of the general formula wherein R 1 and R 2 each represent a hydrogen atom or an alkyl group containing 1, 2 or 3 carbon atoms and wherein n represents an anteger greater than 3. Such materials may be prepared as described in Belgium Patent 817,678. Also are poly- lactones prepared from the hydroxy acids as described in British Patent 1,425,307.
  • a method of making the detergent composition of the invention comprising the steps of spray drying a crutcher mix' containing the anionic, cationic and builder components and subsequently absorbing the nonionic surfactant in liquid or molten form into the spray-dried granules.
  • This process is particularly valuble when the builder comprises an aluminosilicate ion-exchange material.
  • compositions comprising aluminosilicate builder the nonionic is included in the crutcher mix for spray drying, but the components of the surfactants are premixed before addition of the aluminosilicate.
  • the anionic and nonionic surfactants and the builder and filler components can be spray dried in conventional manner to form a base powder composition and the cationic component can then be added to the base powder either as an approximately 1:1 mixture with part of the builder or filler components retained for that purpose, or as an inclusion complex of, for instance, urea.
  • the cationic surfactant can be sprayed onto the base powder, or added as a dry mixed prill agglo- meratedwith an inorganic or organic agglomerating aid, or can be separately spray dried and added to the base powder as a dry mixed granule.
  • the cationic surfactant and base powder compositions can be individually spray dried in separate stages of a multi-stage spray drying tower.
  • compositions of the invention can also be provided in the form of two or more component products, which arc either mixed before use or added separately to a laundry solution to provide a concentration of the ternary surfactant system of from about 100 to about 3000 p.p.m., especially from about 500 to about 1500 p.p.m.
  • Each component product includes one or more of the active ingredients of the ternary surfactant system and a mixture of the products in prescribed amounts should have the requisite granular form.
  • one product is formulated as a conventional anionic or nonionic detergent composition suitable for use in the main washcycle of an automatic laundry or washing machine, and the other is formulated as a cationic containing additiv or booster product for use simultaneously with the conventional detergent during the main wash.
  • the additive product will contain nonionic and/or anionic surfactant such that the total composition formed by mixing the component products in specified amounts has the requisite ternary active system.
  • compositions of the invention can also be formulated as special prewash compositions designed for used before the main.wash stage of the conventional laundering cycle.
  • Such prewash composition will normally consist of a single product component containing the defined ternary active system.
  • compositions were prepared by spray-drying an aqueous slurry of the ingredients except for the Dobanol derived nonicnic surfactants which were sprayed onto the spray-dried granules, and the sodium perborate and enzyme which were dry mixed into the composition.
  • lauryl or myristyl trimethyl ammonium chloride in the above examples can be replaced by molar equivalnets of lauryl or myristyl-trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, coconut alkyl benzyl dimethyl ammonium chloride, C 12 alkylbenzyl dimethyl ethyl ammonium chloride, C 12 alkylbenzyl trimethyl ammonium chloride or one of the following compounds -
  • Dobanol 45-E-7 is replaced by a C 14-15 alcohol polyethoxylate containing an average of 6 moles of ethylene oxide, a C 12-15 alcohol polyethoxylate containing an'average .of 6 .
  • Gantrez AN 119 is replaced by, as their sodium salts, a copolymer of methyl methacrylate and maleic acid, the molar ratio of the monomers being about 1:1, of molecular weight about 10,000; an ethylene-maleic acid copolymer of molecular weight about 4,000, a propylene-maleic acid copolymer of molecular weight about 30,000; 1-hexene-maleic acid copolymer of molecular weight about 30,000; 1-hexene-maleic acid copolymer of molecular weight about 25,000; a vinyl pyrrolidone-maleic acid copolymer of molecular weight about 26,000 a styrene-maleic acid copolymer of acrylic acid and itaconic acid; a 1:4 copolymer of 3-butenoic acid and methylenemalonic acid; a 1:1.9 copolymer of methacrylic acid and aconitic acid; and a 1.2:1 copolymer of methyl
  • The- myristyl trimethyl ammonium chloride in the above examples can be replaced by molar equivalnets of lauryl or myristyl-trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, coconut alkyl benzyl dimethyl ammonium chloride, C 12 , alkylbenzyl dimethyl ethyl ammonium chloride, C 12 alkylbenzyl trimethyl ammonium chloride or one of the following compounds

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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)
EP78200050A 1977-06-29 1978-06-20 Solid detergent composition for improved greasy soil removal Withdrawn EP0000225A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2727677 1977-06-29
GB2727577 1977-06-29
GB2727677 1977-06-29
GB2727577 1977-06-29

Publications (1)

Publication Number Publication Date
EP0000225A1 true EP0000225A1 (en) 1979-01-10

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EP78200050A Withdrawn EP0000225A1 (en) 1977-06-29 1978-06-20 Solid detergent composition for improved greasy soil removal

Country Status (13)

Country Link
EP (1) EP0000225A1 (enrdf_load_stackoverflow)
JP (1) JPS5439417A (enrdf_load_stackoverflow)
AT (1) AT400244B (enrdf_load_stackoverflow)
AU (1) AU525063B2 (enrdf_load_stackoverflow)
BR (1) BR7804163A (enrdf_load_stackoverflow)
CH (1) CH643881A5 (enrdf_load_stackoverflow)
DE (1) DE2857163A1 (enrdf_load_stackoverflow)
FR (1) FR2423537A1 (enrdf_load_stackoverflow)
GR (1) GR63770B (enrdf_load_stackoverflow)
IT (1) IT1097286B (enrdf_load_stackoverflow)
MX (1) MX147454A (enrdf_load_stackoverflow)
NL (1) NL7815015A (enrdf_load_stackoverflow)
SE (1) SE446460B (enrdf_load_stackoverflow)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2938731A1 (de) * 1978-09-27 1980-04-03 Unilever Nv Bleich- und reinigungsmittel
EP0051986A3 (en) * 1980-11-06 1982-07-21 The Procter & Gamble Company Detergent compositions
EP0085448A1 (en) * 1982-01-25 1983-08-10 The Procter & Gamble Company Detergent compositions
GB2125814A (en) * 1982-07-05 1984-03-14 Lion Corp Additive composition for granular detergent
US4698167A (en) * 1983-08-11 1987-10-06 The Procter & Gamble Company Detergent with fabric softener
US4744911A (en) * 1985-08-01 1988-05-17 The Procter & Gamble Company Dispersible fabric softeners
US4758378A (en) * 1986-04-23 1988-07-19 The Procter & Gamble Company Softening detergent compositions containing amide softening agent
WO1992008837A3 (en) * 1990-11-16 1992-07-09 Akzo Nv Biodegradable fabric softeners
EP0146289B1 (en) * 1983-11-29 1993-06-02 The Procter & Gamble Company Laundry compositions
GB2303144A (en) * 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
EP0842246A4 (en) * 1995-07-08 2000-01-12 Procter & Gamble DETERGENT COMPOSITION COMPRISING A CATIONIC ESTER SURFACTANT AND A PROTEASE
WO2000034423A1 (en) * 1998-12-10 2000-06-15 Unilever Plc Detergent compositions
WO2001027231A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
US6395696B2 (en) 2000-06-02 2002-05-28 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions containing a cationic detergent and builder
WO2002048297A1 (en) * 2000-12-15 2002-06-20 Unilever Plc Detergent compositions
US6720298B2 (en) 2000-12-15 2004-04-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions comprising an ethoxylated alcohol and alkyl ioenzene sulfonate
EP1294410A4 (en) * 2000-04-07 2004-11-17 Novapharm Res Australia METHOD AND COMPOSITION FOR CLEANING MEDICAL INSTRUMENTS
WO2011151167A1 (en) * 2010-05-31 2011-12-08 Unilever Nv Laundry treatment composition
WO2018078603A1 (en) * 2016-10-31 2018-05-03 Sabic Global Technologies B.V. Formula for superior detergency and anti re-deposition benefit

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH636123A5 (de) * 1978-06-07 1983-05-13 Ciba Geigy Ag Verfahren zur herstellung schaumregulierter waschmittel.
JPS5822079B2 (ja) * 1979-06-29 1983-05-06 花王株式会社 洗剤組成物
JPS59145300A (ja) * 1983-02-07 1984-08-20 日本パ−オキサイド株式会社 漂白洗剤
JPS6084397A (ja) * 1983-10-17 1985-05-13 花王株式会社 洗浄剤組成物
GB8413802D0 (en) 1984-05-30 1984-07-04 Procter & Gamble Detergent with suds control
ZA857810B (en) * 1984-10-17 1987-05-27 Colgate Palmolive Co Softening and anti-static liquid detergent composition
GR870086B (en) * 1986-01-27 1987-05-28 Colgate Palmolive Co Detergent softener compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1220956B (de) * 1964-04-21 1966-07-14 Henkel & Cie Gmbh Maschinenwaschmittel
LU53736A1 (enrdf_load_stackoverflow) * 1966-05-23 1968-02-21
FR2073557A5 (fr) * 1969-12-10 1971-10-01 Gillette Co Compositions pour le lavage du linge,provoquant simultanement le nettoyage et l'adoucissage
DE2025944A1 (en) * 1970-05-27 1971-12-09 Henkel & Cie GmbH, 4000 Dusseldorf Detergent compsns for textiles - with combined cleaning - and softening actions,contng quaternary ammonium salts of unsatd carb
FR2236925A1 (en) * 1973-07-13 1975-02-07 Colgate Palmolive Co Dual purpose detergent softening compsn. - contg. a mixture of anionic, non-ionic, cationic surfactants with a phosphate detergent
FR2272167A1 (enrdf_load_stackoverflow) * 1974-05-20 1975-12-19 Berol Kemi Ab

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1220956B (de) * 1964-04-21 1966-07-14 Henkel & Cie Gmbh Maschinenwaschmittel
LU53736A1 (enrdf_load_stackoverflow) * 1966-05-23 1968-02-21
FR2073557A5 (fr) * 1969-12-10 1971-10-01 Gillette Co Compositions pour le lavage du linge,provoquant simultanement le nettoyage et l'adoucissage
DE2025944A1 (en) * 1970-05-27 1971-12-09 Henkel & Cie GmbH, 4000 Dusseldorf Detergent compsns for textiles - with combined cleaning - and softening actions,contng quaternary ammonium salts of unsatd carb
FR2236925A1 (en) * 1973-07-13 1975-02-07 Colgate Palmolive Co Dual purpose detergent softening compsn. - contg. a mixture of anionic, non-ionic, cationic surfactants with a phosphate detergent
FR2272167A1 (enrdf_load_stackoverflow) * 1974-05-20 1975-12-19 Berol Kemi Ab

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2938731A1 (de) * 1978-09-27 1980-04-03 Unilever Nv Bleich- und reinigungsmittel
EP0051986A3 (en) * 1980-11-06 1982-07-21 The Procter & Gamble Company Detergent compositions
EP0085448A1 (en) * 1982-01-25 1983-08-10 The Procter & Gamble Company Detergent compositions
GB2125814A (en) * 1982-07-05 1984-03-14 Lion Corp Additive composition for granular detergent
US4698167A (en) * 1983-08-11 1987-10-06 The Procter & Gamble Company Detergent with fabric softener
EP0146289B1 (en) * 1983-11-29 1993-06-02 The Procter & Gamble Company Laundry compositions
US4744911A (en) * 1985-08-01 1988-05-17 The Procter & Gamble Company Dispersible fabric softeners
US4758378A (en) * 1986-04-23 1988-07-19 The Procter & Gamble Company Softening detergent compositions containing amide softening agent
WO1992008837A3 (en) * 1990-11-16 1992-07-09 Akzo Nv Biodegradable fabric softeners
GB2303144A (en) * 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
EP0862607A4 (en) * 1995-07-08 1999-08-18 Procter & Gamble DETERGENT COMPOSITIONS
EP0842246A4 (en) * 1995-07-08 2000-01-12 Procter & Gamble DETERGENT COMPOSITION COMPRISING A CATIONIC ESTER SURFACTANT AND A PROTEASE
WO2000034423A1 (en) * 1998-12-10 2000-06-15 Unilever Plc Detergent compositions
WO2001027231A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
EP1294410A4 (en) * 2000-04-07 2004-11-17 Novapharm Res Australia METHOD AND COMPOSITION FOR CLEANING MEDICAL INSTRUMENTS
US7217684B2 (en) 2000-04-07 2007-05-15 Alex Sava Process and composition for cleaning medical instruments
US6395696B2 (en) 2000-06-02 2002-05-28 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions containing a cationic detergent and builder
US6689735B2 (en) 2000-12-15 2004-02-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
US6759380B2 (en) 2000-12-15 2004-07-06 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
US6720298B2 (en) 2000-12-15 2004-04-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions comprising an ethoxylated alcohol and alkyl ioenzene sulfonate
WO2002048297A1 (en) * 2000-12-15 2002-06-20 Unilever Plc Detergent compositions
WO2011151167A1 (en) * 2010-05-31 2011-12-08 Unilever Nv Laundry treatment composition
CN103201366A (zh) * 2010-05-31 2013-07-10 荷兰联合利华有限公司 洗衣处理组合物
CN103201366B (zh) * 2010-05-31 2015-03-18 荷兰联合利华有限公司 洗衣处理组合物
WO2018078603A1 (en) * 2016-10-31 2018-05-03 Sabic Global Technologies B.V. Formula for superior detergency and anti re-deposition benefit
US11466232B2 (en) 2016-10-31 2022-10-11 Sabic Global Technologies B.V. Formula for superior detergency and anti re-deposition benefit

Also Published As

Publication number Publication date
AU525063B2 (en) 1982-10-21
IT1097286B (it) 1985-08-31
GR63770B (en) 1979-12-15
FR2423537A1 (fr) 1979-11-16
JPS5439417A (en) 1979-03-26
AU3758778A (en) 1980-01-03
NL7815015A (nl) 1979-10-31
FR2423537B1 (enrdf_load_stackoverflow) 1981-12-31
ATA469178A (de) 1986-12-15
CH643881A5 (de) 1984-06-29
DE2857163C2 (enrdf_load_stackoverflow) 1989-12-14
IT7825093A0 (it) 1978-06-28
MX147454A (es) 1982-12-03
BR7804163A (pt) 1979-02-20
AT400244B (de) 1995-11-27
SE446460B (sv) 1986-09-15
SE7907257L (sv) 1979-08-31
DE2857163A1 (de) 1980-03-06

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