EP0085448B2 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

Info

Publication number
EP0085448B2
EP0085448B2 EP19830200064 EP83200064A EP0085448B2 EP 0085448 B2 EP0085448 B2 EP 0085448B2 EP 19830200064 EP19830200064 EP 19830200064 EP 83200064 A EP83200064 A EP 83200064A EP 0085448 B2 EP0085448 B2 EP 0085448B2
Authority
EP
European Patent Office
Prior art keywords
surfactant
weight
acid
cosurfactant
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19830200064
Other languages
German (de)
English (en)
Other versions
EP0085448A1 (fr
EP0085448B1 (fr
Inventor
Brian Garston
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10527839&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0085448(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Ltd, Procter and Gamble Co filed Critical Procter and Gamble Ltd
Publication of EP0085448A1 publication Critical patent/EP0085448A1/fr
Publication of EP0085448B1 publication Critical patent/EP0085448B1/fr
Application granted granted Critical
Publication of EP0085448B2 publication Critical patent/EP0085448B2/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—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 granular 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 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 granular 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, zwiterionic 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 4% to 25%, and especially from 8% to 20%.
  • the auxiliary surfactant system is preferably from 1 % to 4% of the detergent composition with the amine oxide and quaternary ammonium surfactants being present at a weight ratio of from 3:1 to 1:3, with the individual cosurfactants each preferably constituting up to 1.5% by weight of composition.
  • the weight ratio of surfactant:cosurfactant is at least 1:1, preferably from 2:1 to 50:1, more preferably from 3:1 to 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 20:1 to 1:5, more preferably from 6:1 to 1:3, especially from 5:1 to 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 have 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 have 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.
  • Highly suitable nonionic surfactants of this type have the general formula RO(CH 2 CH 2 O) 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 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 8.5 to 11.
  • 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 S - 1s ) 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, 1 - 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-
  • 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.
  • Naphthenic 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.
  • 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 from 10 to 14 carbon atoms and each R 1 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 1 is methyl, and R is C 12 -C 14 alkyl.
  • the quarternary 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 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 C 12 -C 14 alkyl.
  • 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 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 diethytenetriaminepenta 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, (ethylene- dioxy) 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; oxydisuccin
  • the builder salts comprise from 5% to 70% by weight of the composition, preferably from 10% to 50% by weight.
  • 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, otpical 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-ylaminostillbene-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, dis
  • 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 SiOp/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 micro- crystalline 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 silica suds controlling agent suitable herein.
  • the silicone material can be represented by alkylated polysiloxane materials such as silica aerogens 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.
  • 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 P0 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 12 -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.
  • 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 spraydried 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 grnaular 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.

Landscapes

  • 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)

Claims (5)

1. Composition détergente granulaire ayant, en dispersion aqueuse à 1 % en poids, un pH d'au moins 7, comprenant:
(a) de 2% à 60% en poids de tensio-actif choisi parmi les tensio-actifs anioniques et leurs mélanges avec des tensio-actifs non ioniques, de type zwitterion et ampholytes;
(b) de 0,5 à 6% en poids de cotensio-actif comprenant un mélange, selon un rapport.pondéral de 5:1 à 1:5, de:
(i) un oxyde d'amine ayant la formule générale I:
Figure imgb0014
dans laquelle R est un groupe alkyle ou alkényle linéaire ou ramifié ayant 10 à 14 atomes de carbone, chaque R1 est choisi, indépendamment, parmi les groupes méthyles et ―(CnH2nO)mH, i est un nombre entier valant de 1 à 6, j vaut 0 ou 1, n est 2 ou 3 et m vaut 1 à 3, la somme totale des groupes CnH2nO n'étant dans une molécule par supérieure à 5, et
(ii) un tensio-actif de type ammonium quaternaire ayant la formule générale II:
Figure imgb0015
dans laquelle R2 est un groupe alkyle, alcényle ou alcaryle linéaire ou ramifié ayant 10 à 14 atomes de carbone et chaque R3 est choisi indépendamment parmi un groupe méthyle et ―(CnH2nO)m, i est un nombre entier valant de 1 à 6, j vaut 0 ou 1, n vaut 2 ou 3 et m vaut 1 à 3, la somme totale des groupes CnH2nO présents dans une molécule n'étant pas supérieure à 5, et Z représente un contre-anion et nombre suffisant pour la neutralité électrique,
le rapport pondéral tensi-actif: cotensio-actif étant au moins égal à 1:1, et la rapport équivalent de tensio-actif anionique:tensio-actif cationique étant aussi au moins égal à 1:1, et
(c) de 5% à 70% en poids d'un sel organique ou minéral adjuvant de détergence.
2. Composition selon la revendication 1, caractérisée en ce que de 1 % à 4% du système de cotensi-actif comprend un oxyde d'amine et un tensio-actif de type ammonium quaternaire, selon un rapport pondéral de 3:1 à 1:3.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que le rapport pondéral tensio-actif:cotensio-actif se situe dans l'intervalle allant de 2:1 à 50:1, de préférence de 3:1 à 20:1.
4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le tensio-actif comprend un mélange de tensio-actifs anionique et non ionique alkoxylé, selon un rapport pondéral de 20:1 à 1:5, de préférene de 6:1 à 1:3, encore mieux de 5:1 à 1:1.
5. Composition détergente granulaire selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comporte de 4 à 25% de ensio-actif, de 1 à 4% de cotensio-actif, de 10% à 50% d'adjuvant de détergence, de 3% à 40% de peroxyde de blanchiment et de 0 à 5% d'un activateur de blanchiment de type peracide organique.
EP19830200064 1982-01-25 1983-01-17 Compositions détergentes Expired EP0085448B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8201948 1982-01-25
GB8201948 1982-01-25

Publications (3)

Publication Number Publication Date
EP0085448A1 EP0085448A1 (fr) 1983-08-10
EP0085448B1 EP0085448B1 (fr) 1985-10-16
EP0085448B2 true EP0085448B2 (fr) 1990-10-10

Family

ID=10527839

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830200064 Expired EP0085448B2 (fr) 1982-01-25 1983-01-17 Compositions détergentes

Country Status (2)

Country Link
EP (1) EP0085448B2 (fr)
DE (1) DE3360996D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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.
WO1997012022A1 (fr) * 1995-09-29 1997-04-03 The Procter & Gamble Company Compositions stables de detergents aqueux pour lessive, comprenant des agents tensio-actifs quaternaires et des oxydes d'amines et presentant des proprietes de suspension ameliorees
DE102010043066A1 (de) * 2010-10-28 2012-05-03 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit antimikrobieller Wirkung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174304A (en) * 1975-08-01 1979-11-13 Bullen Chemical Company Midwest, Inc. Surfactant system
CH643881A5 (de) * 1977-06-29 1984-06-29 Procter & Gamble Detergenskompositionen.
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
EP0060003B1 (fr) * 1981-03-07 1986-06-25 THE PROCTER & GAMBLE COMPANY Compositions pour le traitement de matières textiles et leur préparation

Also Published As

Publication number Publication date
EP0085448A1 (fr) 1983-08-10
DE3360996D1 (en) 1985-11-21
EP0085448B1 (fr) 1985-10-16

Similar Documents

Publication Publication Date Title
US4412934A (en) Bleaching compositions
US4321165A (en) Detergent compositions comprising cationic, anionic and nonionic surfactants
US4732694A (en) Suds suppressor compositions and their use in detergent compositions
US4430243A (en) Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4686062A (en) Detergent composition
EP0174132B1 (fr) Compositions d'activeurs pour le blanchiment, leur préparation et leur usage dans des compositions pour le lavage du linge
EP0046342B1 (fr) Compositions détergentes et procédés pour leur fabrication
US4417994A (en) Particulate detergent additive compositions
US4525292A (en) Bleaching detergent compositions comprising sulfosuccinate bleach promoters
EP0137669B1 (fr) Compositions détergentes
EP0000225A1 (fr) Composition détergente solide pour une meilleure élimination des salissures grasses
EP0040038B1 (fr) Compositions détergentes granulaires
EP0091802B1 (fr) Compositions à mousse controlée comme additifs à des détergents et leur utilisation dans des compositions détergentes
EP0051986B1 (fr) Compositions détergentes
EP0085448B2 (fr) Compositions détergentes
EP0095904B1 (fr) Détergents liquides et compositions pour leur utilisation
EP0131393A1 (fr) Systèmes d'émulsionnants de monoester de glycérol dans des compositions détergentes pour l'élimination de la rouillure huileuse
EP0181180B1 (fr) Compositions détergentes

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19840130

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3360996

Country of ref document: DE

Date of ref document: 19851121

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

Effective date: 19860620

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER N.V.

Effective date: 19860714

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC/UNILEVER N.V.

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19901010

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

NLR2 Nl: decision of opposition
ET3 Fr: translation filed ** decision concerning opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960130

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960306

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970131

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 19970131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970801

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970801

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20011214

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020104

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020131

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20030116

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 20030116

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO