EP0782558A1 - Compositions detergentes - Google Patents

Compositions detergentes

Info

Publication number
EP0782558A1
EP0782558A1 EP95934991A EP95934991A EP0782558A1 EP 0782558 A1 EP0782558 A1 EP 0782558A1 EP 95934991 A EP95934991 A EP 95934991A EP 95934991 A EP95934991 A EP 95934991A EP 0782558 A1 EP0782558 A1 EP 0782558A1
Authority
EP
European Patent Office
Prior art keywords
detergent
compositions
acid
compound according
agents
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.)
Ceased
Application number
EP95934991A
Other languages
German (de)
English (en)
Other versions
EP0782558A4 (fr
Inventor
Frederick Edward Hardy
Barry Thomas Ingram
Christian Leo Marie Vermote
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 Co
Original Assignee
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0782558A1 publication Critical patent/EP0782558A1/fr
Publication of EP0782558A4 publication Critical patent/EP0782558A4/fr
Ceased 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • 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
    • C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/146—Sulfuric acid esters
    • 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

  • the present invention relates to detergent compositions comprising a surfactant which provides suds supressing benefits.
  • a particularly desirable performance benefit for detergent compositions is good greasy and oily soil removal over a wide spectrum of temperatures.
  • the detergent manufacture has found it necessary to increase the amount of surfactant incorporated into detergent compositions.
  • the compositions have also tended to become more compact formulations, which is also in line with current trends to produce more compa formulations to reduce the environmental impact.
  • the sudsing profile of a detergent composition is also an importa factor to be considered by the detergent manufacturer. It is generall considered that high sudsing is not a desirable feature of a laundr detergent composition for laundering conducted in automatic washin machines. However, high levels of surfactant in a detergent compositio usually results in an increase in the sudsing of the detergent compositio This problem is particularly acute if the surfactant system comprises hig levels of anionic surfactant. Thus, in order to control the suds profil such compositions require the addition of a suds suppressor. Howeve the suds suppressors currently available are generally expensive and als provide no other performance benefit to the composition other than sud suppression. Therefore, it is desirable that their presence is minimised.
  • the anionic compounds of the prese invention readily hydrolyse in the wash liquor and these hydrolysi products then act as suds suppressors.
  • the hydrolysis products can thu act to suppress the sudsing produced by other surfactants which may b preferred components of the detergent composition.
  • the hydrolysis products tend to be formed in the latter stages of th washing process, when sudsing is at its greatest and suds suppression i most required.
  • another advantage of the presence of th suds suppressing hydrolysis products is that the amount of addition suds suppressor required in the formulation is reduced.
  • the anioni compounds of the present invention have a dual function as a compone of a surfactant system providing improved cleaning and as precursors o suds suppression agents in detergent compositions.
  • a further advantage of the anionic compounds of the present invention is that they are also low sudsing compounds per se.
  • Liquid detergent compositions comprising branched alkoxylated anionic surfactants for use as suds suppressors have been disclosed in European patent application number 93870123.2.
  • the present invention relates to compounds according to the formula:
  • Ri and R2 are independently C4 to C12 hydrocarbyl, X and Y are independently selected from
  • R 3 and R4 are independently Ci to C4 hydrocarbyl, a and b are independently from 0 to 4, R5 is a C ⁇ to C9 hydrocarbyl or Ci to C9 polyalkylene oxide having an average degree of polymerization of from 1 to 9, d is 0 to 2, Q is an anionic group, and M is a cation providing electrical neutrality and mixtures thereof.
  • the present invention also relates to detergent compositions comprising at least 0.1 % of a compound according to any of the preceding claims and at least 0.1 % of a detergent ingredient selected from surfactants builders and chelants and mixtures thereof.
  • the present invention also relates to a method of washing fabrics comprising contacting said fabrics with an aqueous solution comprising at least 0.005% of the compound or at least 0.1 % of the detergent compositions of the present invention.
  • the present invention is an anionic compound which provides th dual benefits of improved oily and greasy soil removal and of sud suppresion.
  • said compound is according to th formula:
  • Ri and R2 are independently C4 to C12 , preferably ⁇ to C12 more preferably C to Cio hydrocarbyl, selected form alkyl, alkenyl an alkylaryl groups and which may be branched or linear.
  • Ri anohydrocarbyl selected form alkyl, alkenyl an alkylaryl groups and which may be branched or linear.
  • R2 are independently alkyl groups.
  • the sum of the carbon chain lengths of J and R2 is from 10 t 18, more preferably from 12 to 18 and the difference in said carbon chai lengths of Rj and R2 is 4 or less, preferably 3 or less, most preferably or less.
  • Ri and R2 are independently C to Cio linear alkyl groups, most preferably having the same number o carbon atoms.
  • X and Y are independentl selected from
  • — O— C— O — , — C — O and — O — C and c is 0 or 1 preferably zero.
  • R3 and R4 are independentl Ci to C4, preferably linear Ci to C2 hydrocarbyl.
  • a and b ar independently from 0 to 4, preferably from 0 to 2.
  • R5 is a C ⁇ to Ci8, preferably a Cito C9 hydrocarbyl selected from alkyls, alkenyls, and alkylaryls, or a Cj to C9 polyalkylene oxide, preferably ethylene or propylene having an average degree of polymerization of from 1 to 9.
  • d is 0 to 2.
  • Q is any anionic group.
  • Suitable anionic groups for use herein may be selected from sulphates, sulphonates and carboxylates.
  • compositions of the present invention are preferably substantially free of compounds containing about 13 or more ethylene oxide groups. These compounds tend to be relatively non-biodegradable, do not enhance the cleaning or fabric conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them. It is to be noted that polyethoxylated surfactants having relatively low levels of ethoxylation, such as those described above, exhibit better biodegradability characteristics and may be advantageously included in the compositions of the present invention.
  • M is a counter ion and may be any cation which results in the compound becoming water dispersible.
  • the counterions are present in an appropriate number to give electrical neutrality.
  • Suitable cations may be selected from metal ions such as sodium, potassium, lithium, calcium, magnesium, ammonium or substituted ammonium.
  • substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof.
  • Preferred anionic surfactants for use herein are according to the formulae: R
  • anionic surfactants can b synthesised by methods known in the art.
  • the anionic surfactants undergo hydrolysis at the ester or carbonate ester linkage, during the wash process yielding the corresponding fatty acids or alcohols. These hydrolysis products also act as suds suppressors.
  • Another embodiment of the present invention is a detergent composition
  • a detergent composition comprising at least 0.1 %, preferably from 0.5% to 40%, most preferably from 0.5% to 20% of the compound of the present invention and at least 0.1 %, preferably from 3% to 99.9% of a detergent ingredient selected from surfactants, builders, chelants and mixtures thereof.
  • the detergent composition may preferalby comprise surfactants.
  • surfactants useful herein include the conventional CJ I-CIS alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulphates ("AS”), the Cl0"Cl8 secondary (2,3) alkyl sulphates of the formula CH3(CH2) ⁇ (CHOS ⁇ 3 " M + ) CH3 and CH3 (CH2) y (CHOS ⁇ 3 ⁇ M + ) CH2CH3 where x and (y -I- 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the alkyl alkoxy sulphates ("AE X S”; especially EO 1-7 ethoxy sulphates), Cio-Cis alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarbox
  • the conventional nonionic and amphoteric surfactant such as the C12-C18 alkyl ethoxylates ("AE") including the so-calle narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylate (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines an sulphobetaines ("sultaines"), C10-C18 amine oxides, and the like, ca also be included in the overall compositions.
  • the C10-C1 N-alk polyhydroxy fatty acid amides can also be used. Typical examples included the C12-C18 N-methylglucamides. See WO 9,206,154.
  • suga derived surfactants include the N-alkoxy polyhydroxy fatty acid amide such as C10-C1 N-(3-methoxypropyl) glucamide.
  • the N-propyl throug N-hexyl C12-C1 glucamides can be used for low sudsing.
  • C10-C2 conventional soaps may also be used. If high sudsing is desired, th branched-chain C10-C16 soaps may be used. Mixtures of anionic an nonionic surfactants are especially useful.
  • Other conventional usef surfactants such as cationics are listed in standard texts.
  • compositions comprise fro 1 % to 80%, preferably from 5% to 50%, most preferably from 10% t 40% of a surfactant.
  • Preferred surfactants for use herein are linear alky benzene sulphonate, alkyl sulphates and alkyl alkoxy lated nonionics o mixtures thereof.
  • Detergent builders can optionally be included in the composition herein to assist in controlling mineral hardness. Inorganic as well a organic builders can be used. Builders are typically used in fabri laundering compositions to assist in the removal of paniculate soils.
  • the level of builder can vary widely depending upon the end use o the composition and its desired physical form. When present, th compositions will typically comprise at least 1 % builder. Liqui formulations typically comprise from 5% to 50%, more typically abou 5% to 30%, by weight, of detergent builder. Granular formulation typically comprise from 10% to 80%, more typically from 15% to 50 by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si2 ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + l*yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • magnesium silicate which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the .empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • poly carboxy late refers to compounds having a plurality of carboxy late groups, preferably at least 3 carboxy lates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypoly carboxy lates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builde examples include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the lik Laurylsuccinates are the preferred builders of this group, and a described in European Patent Application 86200690.5/0,200,26 published November 5, 1986.
  • Fatty acids e.g., C12-C1 monocarboxylic acids
  • t aforesaid builders especially citrate and/or the succinate builders, t provide additional builder activity.
  • Such use of fatty acids will generall result in a diminution of sudsing, which should be taken into account b the formulator.
  • the detergent compositions herein may also optionally contain on or more iron and/or manganese chelating agents.
  • chelating agen can be selected from the group consisting of amino carboxy lates, amin phosphonates, polyfunctionally-substituted aromatic chelating agents an mixtures therein, all as hereinafter defined. Without intending to be boun by theory, it is believed that the benefit of these materials is due in part t their exceptional ability to remove iron and manganese ions from washin solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents included ethy lenediaminetetracetates , N-hydroxyethylethylenediaminetriacetates nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines alkali metal, ammonium, and substituted ammonium salts therein an mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5- disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from .1 % to 10% more preferably, from 0.1 % to 3.0% by weight of such compositions.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Peroxygen bleaching agents can also be used. Suitable peroxyge bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphat peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having a average particle size in the range from about 500 micrometers to abou 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water- soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, e.g., sodium perborate (e.g., mono- or tetra-hydrate) , the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., mono- or tetra-hydrate
  • nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6- nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containin from 1 to about 12 carbon atoms.
  • Highly preferred lactam activator include benzoyl caprolactam, octanoyl caprolactam, 3,5,5 trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoy caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoy valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoy valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985 incorporated herein by reference, which discloses acyl caprolactams including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are als known in the art and can be utilized herein.
  • One type of non-oxyge bleaching agent of particular interest includes photoactivated bleachin agents such as the sulfonated zinc and/or aluminum phthalocyanines. Se U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used detergent compositions will typically contain from 0.025% to 1.25%, b weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of manganese compound.
  • manganese compound Such compounds are well known in the art an include, for example, the manganese-based catalysts disclosed in U.S Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1 544,440A2, and 544,490A1; Preferred examples of these catalysts included Mn ⁇ t ⁇ -Ot ⁇ O ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(PF6)2,
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
  • the polyoxyethylene segments of (a)(i) will have a degre of polymerization of from about 200, although higher levels can be used preferably from 3 to about 150, more preferably from 6 to about 100
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are no limited to, end-caps of polymeric soil release agents such a M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer fro 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 t Gosselink.
  • Polymeric soil release agents useful in the present invention als include cellulosic derivatives such as hydroxyether cellulosic polymers copolymeric blocks of ethylene terephthalate or propylene terephthalat with polyethylene oxide or polypropylene oxide terephthalate, and th like. Such agents are commercially available and include hydroxyethers o cellulose such as METHOCEL (Dow). Cellulosic soil release agents fo use herein also include those selected from the group consisting of C1-C alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issue December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophob segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 viny esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxid backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C1-C6 viny esters
  • poly (vinyl acetate) grafted onto polyalkylene oxid backbones such as polyethylene oxide backbones.
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters. If utilized, soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the detergent compositions herein, typically from 0.1 % to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01 % to 5%.
  • the most preferred soil release and anji-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil relea peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared polymerizing or copolymerizing suitable unsaturated monomer preferably in their acid form.
  • Unsaturated monomeric acids that can polymerized to form suitable polymeric polycarboxylates include acryl acid, maleic acid (or maleic anhydride), fumaric acid, itaconic aci aconitic acid, mesaconic acid, citraconic acid and methylenemalonic aci
  • the presence in the polymeric polycarboxylates herein or monomer segments, containing no carboxy late radicals such as vinylmethyl ethe styrene, ethylene, etc. is suitable provided that such segments do n constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be deriv from acrylic acid.
  • acrylic acid-based polymers which are usef herein are the water-soluble salts of polymerized acrylic acid.
  • T average molecular weight of such polymers in the acid form preferab ranges from about 2,000 to 10,000, more preferably from about 4,000 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble sal of such acrylic acid polymers can include, for example, the alkali meta ammonium and substituted ammonium salts. Soluble polymers of this ty are known materials. Use of polyacry lates of this type in deterge compositions has been disclosed, for example, in Diehl, U.S. Pate 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferr component of the dispersing/anti-redeposition agent.
  • Such materia include the water-soluble salts of copolymers of acrylic acid and male acid.
  • the average molecular weight of such copolymers in the acid for preferably ranges from about 2,000 to 100,000, more preferably fro about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • T ratio of acrylate to maleate segments in such copolymers will general range from about 30:1 to about 1:1, more preferably from about 10:1 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers c include, for example, the alkali metal, ammonium and substitut ammonium salts.
  • Soluble acrylate/maleate copolymers of this type a known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acry lie/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include poly vinyl pyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP- A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2 hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2 hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is salt-forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4', bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'- stilbenedisulfonic acid and disodium salt.
  • This particular brightene species is commercially marketed under the tradename Tinopal-UNPA GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferre hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4' bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2' -stilbenedisulfonic acid disodium salt.
  • This particula brightener species is commercially marketed under the tradename Tinopa 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is morphilino and is a cation such as sodium
  • the brightener is 4,4 * -bis[(4-anilino-6 morphilino-s-triazine-2-yl)amino]2, 2' -stilbenedisulfonic acid, sodium salt
  • This particular brightener species is commercially marketed under th tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in th present invention provide especially effective dye transfer inhibitio performance benefits when used in combination with the selecte polymeric dye transfer inhibiting agents hereinbefore described. Th combination of such selected polymeric materials (e.g., PVNO and/o PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • selected polymeric materials e.g., PVNO and/o PVPVI
  • selected optical brighteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • the detergent composition may comprise any other ingredients commonly employed in conventional detergent compositions such as soaps, suds suppressors, dye transfer inhibitors, perfumes, softeners, brighteners, enzymes and enzyme stabilisers.
  • the detergent compositions which may be in granular, liquid or bar form, may be prepared by combining the ingredients in the required amounts in any suitable order by conventional means.
  • any conventional technique employed in the manufacture of detergent compositions may be used.
  • a further aspect of the present invention is a method of washing fabrics wherein fabrics are contacted with an aqueous solution comprising at least 0.005% of the compound of the present invention or at least 0.1 % of the detergent composition of the present invention.
  • the granular detergent compositions given in examples 1-10 are prepared by combining the listed ingredients in the given proportions.

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Abstract

L'invention concerne des composés anioniques et leur utilisation dans des compositions détergentes. Ces composés présentent le double avantage de capacité tensioactive et de suppression de l'effet moussant.
EP95934991A 1994-09-22 1995-09-18 Compositions detergentes Ceased EP0782558A4 (fr)

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GB9419115 1994-09-22
GB9419115A GB9419115D0 (en) 1994-09-22 1994-09-22 Detergent compositions
PCT/US1995/011798 WO1996009273A1 (fr) 1994-09-22 1995-09-18 Compositions detergentes

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ATE300603T1 (de) * 1995-03-11 2005-08-15 Procter & Gamble Wasch- und reinigungsmittel enthaltend wasserstoffperoxidquelle und protease

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FR1447238A (fr) * 1964-05-05 1966-07-29 Hoechst Ag Agents réducteurs de mousse

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DE3666585D1 (en) * 1985-05-07 1989-11-30 Akzo Nv P-sulphophenyl alkyl carbonates and their use as bleaching activators
US5252770A (en) * 1989-06-05 1993-10-12 Monsanto Company Process for the production of carbonate esters

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Publication number Priority date Publication date Assignee Title
FR1447238A (fr) * 1964-05-05 1966-07-29 Hoechst Ag Agents réducteurs de mousse

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EP0782558A4 (fr) 1999-03-17

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