EP0578872B1 - Compositions de détergents - Google Patents

Compositions de détergents Download PDF

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Publication number
EP0578872B1
EP0578872B1 EP92202170A EP92202170A EP0578872B1 EP 0578872 B1 EP0578872 B1 EP 0578872B1 EP 92202170 A EP92202170 A EP 92202170A EP 92202170 A EP92202170 A EP 92202170A EP 0578872 B1 EP0578872 B1 EP 0578872B1
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EP
European Patent Office
Prior art keywords
paste
bis
dye
detergent
brightener
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 - Lifetime
Application number
EP92202170A
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German (de)
English (en)
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EP0578872A1 (fr
Inventor
Benny De Ryck
Paul Van Dijk
Jose Luis Vega
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
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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
Priority to EP92202170A priority Critical patent/EP0578872B1/fr
Priority to DE69227311T priority patent/DE69227311T2/de
Priority to ES92202170T priority patent/ES2121814T3/es
Priority to AT92202170T priority patent/ATE172240T1/de
Priority to DK92202170T priority patent/DK0578872T3/da
Priority to PCT/US1993/005888 priority patent/WO1994002574A1/fr
Priority to JP50445894A priority patent/JP3560340B2/ja
Priority to AU46421/93A priority patent/AU4642193A/en
Priority to US08/367,289 priority patent/US5529710A/en
Priority to CA002140285A priority patent/CA2140285C/fr
Priority to PH46485A priority patent/PH31248A/en
Priority to EG43693A priority patent/EG20369A/xx
Priority to MA23231A priority patent/MA22931A1/fr
Priority to MX9304261A priority patent/MX9304261A/es
Priority to IE052093A priority patent/IE930520A1/en
Priority to TR00613/93A priority patent/TR28449A/xx
Priority to CN93109880A priority patent/CN1054631C/zh
Publication of EP0578872A1 publication Critical patent/EP0578872A1/fr
Application granted granted Critical
Publication of EP0578872B1 publication Critical patent/EP0578872B1/fr
Priority to CN99110039A priority patent/CN1094512C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • High active detergent granules are by agglomeration of high active pastes consisting of the salts of anionic surfactants with detergent powders. Such pastes have rarely been handled before in the detergent industry for various reasons, including the practical difficulties in handling high viscosity pastes and the need to maintain high temperatures in order to prevent solidification of the material, and the problems associated with discoloration.
  • bleaching agents there is a variety of bleaching agents potentially available for this purpose but only sodium hypochlorite and hydrogen peroxide have commercial importance.
  • Sodium hypochlorite is a more convenient and efficient bleach than hydrogen peroxide.
  • chlorine-based bleach may be undesirable due to the potential to generate sensitisers during the process of some feedstocks.
  • hydrogen peroxide may be used, but is less cost-efficient and can cause process control difficulties due to excessive foaming caused by the liberation of oxygen during bleaching.
  • GB-A-1 369 269 published on October 2nd, 1974, describes a process of dry neutralisation for making detergent granules. It says that various difficulties are encountered including local discoloration of the organic detergent. However no solutions are specifically given to this problem.
  • GB-A-2 221 695 published on February 14th, 1990, also describes a dry neutralisation process. It says that various adjuvants may be added with the neutralising agent, but there are no benefits suggested from adding brighteners or dyes, apart from it being a convenient process route for many adjuvants.
  • GB-A-2 166 452 published on May 8th, 1986, describes a processing route which involves dispersing organic materials with particles of an inorganic component to form solid pellets which may then be granulated.
  • a wide choice of detergent ingredients which may be added upon neutralisation is suggested, including, blueing agents, fluorescent dyes and pigments.
  • blueing agents including, blueing agents, fluorescent dyes and pigments.
  • EPA 327 963 published on August 16th, 1989 discloses a method of pre-neutralising the surfactant acids in a slurry, spray-drying the slurry to form a powder and densifying said powder.
  • Brighteners may be incorporated into the slurry as a convenient way of bringing them into the finished composition, but there is no suggestion that this is of benefit to the colour of the densified granules.
  • EP-A-0 508 543 published on 14th October 1992
  • EP-A-0 510 746 published on 28th October 1992
  • EP-A-0 555 622 published on 18th August 1993
  • These applications disclose detergent compositions, and processes for making such compositions from high active detergent pastes.
  • the addition of an optical brightener in the finished detergent composition is disclosed but there is no mention of using dyes or optical brightener in the high active detergent pastes to avoid the discolouration problem.
  • These new processes, based on high active detergent pastes enable manufacture of granules having a higher surfactant activity than before, which may lead to the discoloration problems caused by feedstocks in the form of hot surfactant pastes.
  • composition of a high active paste of detergent salts which comprises specific ingredients which give a very acceptable white appearance to the finished detergent granules.
  • the invention relates to a process for making a high active detergent granule comprising the steps of dispersing organic detergent component, with particles of an inorganic component in the presence of a dye or optical brightener comprising the steps of
  • the invention further relates to a high active detergent paste composition which comprises at least 40% by weight of the composition of the salts of anionic surface active agents, said composition having a viscosity of at least 10 Pa.s when measured at a temperature of 70°C and a shear rate of 25s -1 , further comprises a dye or an optical brightener, or a mixture thereof.
  • the dye or optical brightener is added to the composition either before or during the agglomeration process in a liquid form.
  • a preferred embodiment of this invention is to use either an aqueous solution or an organic carrier medium.
  • the organic carrier is a nonionic surfactant or polyethylene glycol.
  • the granules of the present invention are made by mixing a high active paste comprising the salts of anionic surfactants with detergent powders in a high shear mixer (agglomerator).
  • a high shear mixer agglomerator
  • the effect of the mixer is firstly to fluidise the powder and then to rapidly disperse the surfactant paste into this fluidised powder.
  • the resulting mixture remains in substantially discrete particles at all time. It is not allowed to form into a dough which would cause the high shear mixer to block.
  • a fine dispersion mixing and granulation process takes place under the influence of cutting and mixing tools mounted on a shaft. Suitable paste compositions and processes are described in more detail hereinbelow.
  • the resulting particles are high in surfactant activity and high in bulk density, but still have good flow and non-caking characteristics.
  • the surfactant activity is greater than 40% by weight of the particles, and the bulk density is at least 600 g/l.
  • the dye or optical brightener in a liquid form may be either premixed with the high active detergent paste by means of a batch mix tank or continuously into an extruder or into a neutralisation loop, or it may be sprayed or pumped directly into the high shear mixer where it will be dispersed into the particles formed therein.
  • the dye or optical brightener is pumped directly into the neutralisation loop in which the acid forms of the surfactant are being neutralised.
  • Suitable dyes and optical brighteners for the present invention are those that emit light in the violet or blue range of the spectrum.
  • the light emitted by these dyes lies mostly (at least 70%) in the region of visible light below 500nm wavelength.
  • useful dyes include Levanyl Violet BNZ (Trade Name) and Special Fast Blue G FW Ground (Trade Name), both supplied by Bayer AG.
  • Preferred optical brighteners are chosen from the sodium salts of:
  • optical brighteners which are also preferred for use in the present invention include the derivatives of bis-benzoxazolyl and 1,3-diphenyl-2-pyrazoline.
  • the levels of dyes used in the detergent paste is usually less than 20ppm, preferably from 0.1 to 20 ppm. (These levels are referred to as parts per million of pure dye, although normally such dyes are supplied as solutions).
  • the level of optical brightener in the surfactant paste is generally less than 5% and preferably less than 2%.
  • the level of optical brightener in the granular detergent component or composition is typically less than 2%, preferably less than 1%.
  • One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant.
  • the anionic surfactant is preferably as concentrated as possible, (that is, with the lowest possible moisture content possible that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable. While granulation using various pure or mixed surfactants is known, for the present invention to be of practical use in industry and to result in particles of adequate physical properties to be incorporated into granular detergents, an anionic surfactant must be part of the paste in a concentration of above 40%, preferably from 40-95%, and most preferably from 60%-95%.
  • the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
  • the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5 and 20% water.
  • high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
  • Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.
  • Viscosity is a function, among others, of concentration and temperature, with a range in this application from 10 Pa.s to 10,000 Pa.s.
  • the viscosity of the paste entering the system is from 20 to 100 Pa.s. and more preferably from 30 to 70 Pa.s.
  • the viscosity of the paste of this invention is measured at a temperature of 70°C and at a shear rate of 25s -1 .
  • the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C).
  • High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
  • in-line moisture reduction steps e.g. flash drying
  • the activity of the agglomerates is maintained high due to the elimination of moisture.
  • the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size.
  • the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
  • the activity of the aqueous surfactant paste is at least 40% and can go up to about 95%; preferred activities are : 60-95% and 65-80%.
  • the balance of the paste is primarily water but can include various processing aids. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
  • the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
  • the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred.
  • Nonionic surfactants are used as secondary surfactants or processing aids, or as the organic carrier for the optical brightener, and are not included herein as an "active" surfactant.
  • Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980.
  • cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions. The following are representative examples of surfactants useful in the present compositions.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils 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.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11 -C 13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • the acid salts are typically discussed and used, the acid neutralization can be performed as part of the fine
  • the anionic surfactant paste comprises surfactants which are particularly vulnerable to discoloration, such as those pastes comprising at least 5% by weight of linear alkyl benzene sulphonate, methyl ester sulphonate or paraffin sulphonate, or a mixture of these.
  • the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
  • the salt is the surfactant paste discussed throughout this document.
  • the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
  • Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from 0.01:1 to 1:1, more preferably about 0.05:1.
  • Nonionics can be used up to an equal amount of the primary organic surfactant.
  • Such nonionic materials include 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 surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from 4 to 25 moles of ethylene oxide per mole of alkyl phenol and alkyl glucose amides.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 4 to 100 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 80 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
  • Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from 1 to 4; olefin or paraffin sulfonates containing from 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from 3 to 8 moles of
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride. Examples of such trimethyl ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate. Other cationic surfactants including coline esters may be used.
  • Specific preferred surfactants for use herein include: sodium linear C 11 -C 13 alkylbenzene sulfonate; alpha-olefin sulphonates; triethanolammonium C 11 -C 13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g.
  • surfactant means non-nonionic surfactants, unless otherwise specified.
  • the ratio of the surfactant active (excluding the nonionic(s)) to dry detergent builder or powder ranges from 0.005:1 to 19:1, preferably from 0.05:1 to 10:1, and more preferably from 0.1:1 to 5:1. Even more preferred said surfactant active to builder ratios are 0.15:1 to 1:1; and 0.2:1 to 0.5:1).
  • the preferred embodiment of the process of the present invention involves introduction of the anionic surfactant in via pastes as described above, it is possible to have a certain amount via the powder stream, for example in the form of blown powder. In these embodiments, it is necessary that the stickiness and moisture of the powder stream be kept at low levels, thus preventing increased "loading" of the anionic surfactant and, thus, the production of agglomerates with too high of a concentration of surfactant.
  • the liquid stream of a preferred agglomeration process can also be used to introduce other surfactants and/or polymers. This can be done by premixing the surfactant into one liquid stream or, alternatively by introducing various streams in the agglomerator.
  • fine dispersion mixing and/or granulation means mixing and/or granulation of the mixture in a fine dispersion mixer at a blade tip speed of from 5m/sec. to 50 m/sec., unless otherwise specified.
  • the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
  • the more preferred mixing and granulation tip speeds are 10-45 m/sec. and 15-40 m/sec.
  • Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks and esterification reactors.
  • any of a number of mixers/agglomerators can be used.
  • the process of the invention is continuously carried out.
  • mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
  • this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
  • the temperature during the agglomeration is less than 80°C, more preferably between 0° and 70°C, even more preferably between 10 and 60°C and most preferably between 20 and 50°C.
  • Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO 2 , and the like; with a preferred method being solid CO 2 , and the most preferred method being nitrogen cooling.
  • a highly attractive opinion in a preferred embodiment of the present invention to further increase the concentration of surfactant in the final particle is accomplished by the addition to a liquid stream containing the anionic surfactant and/or other surfactant, of other elements that result in increases in viscosity and/or melting point and/or decrease the stickiness of the paste.
  • the addition of these elements can be done in line as the paste is pumped into the agglomerator.
  • Example of these elements can be various powders, described in more detail later herein.
  • the present invention produces granules of high density for use in detergent compositions.
  • a preferred composition of the final agglomerate for incorporation into granular detergents has a high surfactant concentration.
  • the particles/agglomerates made by the present invention are more suitable for a variety of different formulations.
  • These high surfactants containing particle agglomerates require fewer finishing techniques to reach the final agglomerates, thus freeing up large amounts of processing aids (inorganic powders, etc.) that can be used in other processing steps of the overall detergent manufacturing process (spray drying, dusting off, etc).
  • the granules made according to the present invention are large, low dust and free flowing, and preferably have a bulk density of up to 1.0 g/cc, more preferably from 0.6 to 0.8 g/cc.
  • the weight average particle size of the particles of this invention are from 200 to 1000 microns.
  • the preferred granules so formed have a particle size range of from 200 to 2000 microns.
  • the more preferred granulation temperatures range from 10°C to 60°C, and most preferably from 20°C to 50°C.
  • the desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers. If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.
  • the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk.
  • the exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 1-4%.
  • Any compatible detergency builder or combination of builders or powder can be used in the process and compositions of the present invention.
  • the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.4 and z is from 10 to 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from 18% to 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micron to 4 microns.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least 0.13 grams Ca ++ /litre/minute/gram/litre (2 grains Ca ++ /gallon/minute/gram/gallon) of aluminosilicate (anhydrous basis), and generally lies within the range of from 0.13 grams Ca ++ /litre/minute/gram/litre (2 grains/gallon/minute/gram/gallon) to 0.39 grams Ca ++ /litre/minute/gram/litre (6 grains/gallon/minute/gram/gallon), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least 0.26 grams Ca ++ /litre/minute/gram/litre (4 grains/gallon/minute/gram/gallon).
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least 0.065 grams/l/min/g/l (1 grain/gallon/minute/gram/gallon). Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention 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 discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially 27 and has a particle size generally less than 5 microns.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali metal, and especially sodium, salts of the above are preferred.
  • Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO 2 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.
  • the compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.1, 1980, and is preferably free of the latter.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate and perborate, and process acids such as starch, can be used in preferred embodiments of the present invention.
  • organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • compositions of the present invention can be included in the compositions of the present invention. These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, fillers, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.
  • Particulate suds suppressors may also be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by dry adding.
  • the suds suppressing activity of these particles is based on fatty acids or silicones.
  • LAS and AS as used herein mean, respectively, “sodium lauryl benzene sulfonate” and “alkyl sulfate.”
  • MES sodium methyl ester sulphonate.
  • C 45 mean C 14 and C 15 alkyl, unless otherwise specified.
  • TAS means sodium tallow alkyl sulphate.
  • Dobanol 45E7 is a C 14 /C 15 alcohol ethoxylate with 7 units of ethylene oxide and is manufactured by Shell Co.
  • AE3S means sodium alkyl ether sulphate with an average of 3 ethoxy groups per molecule.
  • High active base granules were made from a high active surfactant paste and a powder mixture using a small food processor (Braun [TM] Multipractic Plus Electronic de luxe).
  • the powder mixture consisted of sodium silicate (3 Na) 11.5% sodium carbonate 50.5% carboxy methyl cellulose 1.6% zeolite A 36.4%
  • the high active surfactant paste comprised 18% water, and a total surfactant activity (including optical brightener, when present) of 78%.
  • the anionic surfactants were present in the ratio of 74 : 24 : 2 of LAS : TAS : AE3S.
  • the powdered optical brightener was thoroughly mixed for 15 minutes with the high active surfactant paste inside a Drais (TM) kneader (Planetary mixer and kneading machine type FH1.55 from Draiswerke GmbH), kept at 50°C and with a slight vacuum to avoid aerating the paste.
  • the powdered optical brightener was first thoroughly dispersed in the nonionic surfactant at 50°C using a high speed mixer. This dispersion was then mixed into the high active anionic surfactant paste in the same manner as example 1.
  • the paste was treated in a kneader as in previous examples but no nonionic or brightener was added.
  • the nonionic surfactant was mixed with the anionic surfactant paste in a kneader but no optical brightener was added.
  • agglomerates were sieved between Tyler mesh 20 (corresponding to aperture size of 850 micrometers) and Tyler mesh 35 (corresponding to aperture size of 425 micrometers) to remove the fine and coarse particles, the remaining fraction being assessed for colour by the Hunter Lab method (Hunter, R.S. J.Opt.Soc.Amer 48 597 (1958)) using a commercially available Hunterlab Color/Difference meter model D25-2 from Elscoserv N.V.
  • examples 1-3 containing optical brightener processed as described have the best colour.
  • examples 2 and 3 in which the brightener is premixed with nonionic surfactant have superior colour characteristics.
  • agglomerates were made in a Loedige FM mixer/agglomerator.
  • the powder mixture consisted of: sodium silicate (3 Na) 17.5% sodium carbonate 32.5% carboxy methyl cellulose 2.4% zeolite A 47.6%
  • the high active surfactant paste comprised 18% water, and a total surfactant activity (including dye solution, when present) of 78%.
  • the anionic surfactants were present in the ratio of 74 : 24 : 2 of LAS : TAS : AE3S.
  • a dye solution is prepared consisting of: 2 parts of Special Fast Blue G FW Ground (Acid blue 127/1) supplied by Bayer UK Ltd at a concentration of 25%, and 1 part of Levanyl Violet BNZ (Pigment Violet 23) supplied by Bayer UK Ltd at a concentration of 25%.
  • This dye mixture was then diluted to a 0.1% aqueous solution before mixing with the high active surfactant paste and subsequently processing into agglomerates in the manner described above. 90ml of the 0.1% solution was mixed with 15 kg of paste.
  • agglomerates were sieved between Tyler mesh 20 (corresponding to aperture size of 850 micrometers) and Tyler mesh 35 (corresponding to aperture size of 425 micrometers) to remove the fine and coarse particles, the remaining fraction being assessed for colour by the Hunter Lab method (Hunter, R.S. J.Opt.Soc.Amer 48 597 (1958)) using a commercially available Hunterlab Color/Difference meter model D25-2 from Elscoserv N.V.
  • Example 6 (with dye) has less of a yellow colour than example 7 in which no dye has been added.

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Claims (11)

  1. Procédé pour fabriquer un granulé détergent à haute activité, comprenant les étapes consistant à disperser un constituant détergent organique avec des particules d'un constituant minéral en présence d'un colorant ou d'un azurant optique,
    comprenant les étapes consistant à
    (i) fabriquer une pâte à haute activité comprenant au mois 40% en poids de sels tensioactifs anioniques, par neutralisation des acides correspondants, ladite pâte ayant une viscosité d'au mois 10 Pa.s, lorsqu'elle est mesurée à une température de 70°C et à une vitesse de cisaillement de 25 s-1;
    (ii) granuler ladite pâte à haute activité pour former des agglomérats dans un malaxeur/granulateur à fort cisaillement avec une quantité efficace de poudres de détergent;
    dans lequel
    ou bien le colorant ou l'azurant, ou un mélange des deux, est ajouté sous forme liquide, lors de l'étape (i) du procédé, dans un réacteur en boucle dans lequel les acides détergents anioniques sont neutralisés pour former leurs sels,
    ou bien le colorant ou l'azurant est ajouté sous forme liquide par mélange préalable avec la pâte détergente à haute activité au moyen d'une cuve de mélange maítre ou en continu dans une extrudeuse,
    ou bien le colorant ou l'azurant est pompé ou pulvérisé sous forme liquide, lors de l'étape (ii) du procédé, dans le malaxeur/granulateur à fort cisaillement, en solution aqueuse ou en mélange préalable avec un véhicule.
  2. Procédé selon la revendication 1, dans lequel le colorant ou l'azurant est choisi parmi les colorants ou les azurants qui émettent au moins 70% de lumière dans la région de la lumière visible au-dessous d'une longueur d'onde de 500 nm.
  3. Composition de pâte détergente à haute activité comprenant un colorant ou un azurant optique, ou un mélange des deux,
    caractérisée en ce que
    ladite composition de pâte comprend au moins 40% en poids des sels d'agents tensioactifs anioniques et en ce que la composition de pâte possède une viscosité d'au moins 10 Pa.s, lorsqu'elle est mesurée à une température de 70°C et à une vitesse de cisaillement de 25 s-1.
  4. Composition de pâte détergente à haute activité selon la revendication 3, qui comprend au mois 5% en poids d'alkylbenzènesulfonate linéaire, de méthylestersulfonate, de paraffinesulfonate, ou d'un de leurs mélanges.
  5. Composition selon la revendication 3 ou 4, ledit colorant étant choisi parmi le Levanyl Violet BNZ (marque de commerce) [Pigment Violet 23] et le Special Fast Blue G FW Ground (marque de commerce) [Acid Blue 127/1], tous deux fournis par Bayer AG.
  6. Composition selon l'une quelconque des revendications 3 à 5, ledit colorant étant présent dans une proportion de 0,1 à 5 ppm de la composition de pâte.
  7. Composition selon l'une quelconque des revendications 3 à 6, caractérisée en ce que ledit colorant est ajouté à la composition sous forme d'une solution aqueuse.
  8. Composition selon l'une quelconque des revendications 3 à 7, caractérisée en ce que l'azurant optique est choisi parmi les sels de sodium de:
    4,4'-bis(2-diéthanolamino-4-anilino-s-triazin-6-ylamino)stilbène-2:2'-disulfonate
    4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbène-2:2'-disulfonate
    4,4'-bis(2,4-dianilino-s-triazin-6-ylamino)stilbène-2:2'-disulfonate
    4',4"-bis(2,4-dianilino-s-triazin-6-ylamino)stilbène-2-sulfonate
    4,4'-bis(2-anilino-4-(N-méthyl-N-2-hydroxyéthylamino)-s-triazin-6-ylamino)stilbène-2,2'-disulfonate
    4,4'-bis(4-phényl-2,1,3-triazol-2-yl)stilbène-2,2'-disulfonate
    4,4'-bis(2-anilino-4-(1-méthyl-2-hydroxyéthylamino)-s-triazin-6-ylamino)stilbène-2,2-disulfonate
    4,4'-bis(2-sulfostyryl)biphényle ou
    4,4'-bis(4-chloro-3-sulfostyryl)biphényle
    et/ou l'azurant optique est choisi parmi les dérivés de bis-benzoxazolyle ou
    1,3-diphényl-2-pyrazoline.
  9. Composition selon la revendication 8, caractérisée en ce que en ce que l'azurant est mélangé au préalable avec un véhicule organique avant d'être ajouté à la composition.
  10. Composition selon la revendication 9, caractérisée en ce que le véhicule est un tensioactif non ionique ou du polyéthylèneglycol.
  11. Composition selon l'une quelconque des revendications 3 à 10, ledit azurant optique étant présent dans une proportion de 0,1% à 2% en poids de la composition de pâte.
EP92202170A 1992-07-15 1992-07-15 Compositions de détergents Expired - Lifetime EP0578872B1 (fr)

Priority Applications (18)

Application Number Priority Date Filing Date Title
EP92202170A EP0578872B1 (fr) 1992-07-15 1992-07-15 Compositions de détergents
DE69227311T DE69227311T2 (de) 1992-07-15 1992-07-15 Waschmittelzusammensetzungen
ES92202170T ES2121814T3 (es) 1992-07-15 1992-07-15 Composiciones detergentes.
AT92202170T ATE172240T1 (de) 1992-07-15 1992-07-15 Waschmittelzusammensetzungen
DK92202170T DK0578872T3 (da) 1992-07-15 1992-07-15 Detergentsammensætninger
JP50445894A JP3560340B2 (ja) 1992-07-15 1993-06-18 洗剤組成物
AU46421/93A AU4642193A (en) 1992-07-15 1993-06-18 Detergent compositions
US08/367,289 US5529710A (en) 1992-07-15 1993-06-18 Production of detergent granules with excellent white appearance
CA002140285A CA2140285C (fr) 1992-07-15 1993-06-18 Compositions detergentes
PCT/US1993/005888 WO1994002574A1 (fr) 1992-07-15 1993-06-18 Compositions de detergents
PH46485A PH31248A (en) 1992-07-15 1993-07-08 Production of detergent granules with excellent white appearance.
EG43693A EG20369A (en) 1992-07-15 1993-07-13 Detergent compositions
MA23231A MA22931A1 (fr) 1992-07-15 1993-07-13 Compositions detergentes.
MX9304261A MX9304261A (es) 1992-07-15 1993-07-14 Composiciones detergentes.
IE052093A IE930520A1 (en) 1992-07-15 1993-07-14 Detergent compositions
TR00613/93A TR28449A (tr) 1992-07-15 1993-07-15 Mükemmel bir beyaz görünüme sahip yüksek aktiviteli deterjan terkipleri.
CN93109880A CN1054631C (zh) 1992-07-15 1993-07-15 制备高活性颗粒状洗涤剂的方法
CN99110039A CN1094512C (zh) 1992-07-15 1999-06-25 洗涤剂膏状组合物

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EP92202170A EP0578872B1 (fr) 1992-07-15 1992-07-15 Compositions de détergents

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EP0578872B1 true EP0578872B1 (fr) 1998-10-14

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CA (1) CA2140285C (fr)
DE (1) DE69227311T2 (fr)
DK (1) DK0578872T3 (fr)
EG (1) EG20369A (fr)
ES (1) ES2121814T3 (fr)
IE (1) IE930520A1 (fr)
MA (1) MA22931A1 (fr)
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PH (1) PH31248A (fr)
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US5998351A (en) 1996-03-15 1999-12-07 Amway Corporation Discrete whitening agent particles method of making, and powder detergent containing same

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EP0660873B2 (fr) † 1992-09-01 2006-05-31 The Procter & Gamble Company Detergent en poudre de haute densite
GB9323250D0 (en) * 1993-11-11 1994-01-05 Unilever Plc Process for the production of a detergent composition
US5714456A (en) * 1996-03-15 1998-02-03 Amway Corporation Process for making discrete whitening agent particles
US5714452A (en) * 1996-03-15 1998-02-03 Amway Corporation Whitening agent particle composition
IT1283044B1 (it) * 1996-05-21 1998-04-07 3V Sigma Spa Metodo per la sbianca di detergenti
GB9618877D0 (en) * 1996-09-10 1996-10-23 Unilever Plc Process for preparing high bulk density detergent compositions
DE19855677A1 (de) * 1998-12-02 2000-06-08 Henkel Kgaa Herstellung Aufheller-haltiger Waschmittel-Granulate
GB2364065A (en) * 2000-06-28 2002-01-16 Procter & Gamble Fabric treatment composition
DE10208773A1 (de) * 2002-02-28 2003-09-04 Clariant Gmbh Wässrige Flüssigformulierungen von Pyrazolin-Aufhellern
DE10260833B4 (de) * 2002-12-23 2007-08-16 Henkel Kgaa Verfahren zur Verarbeitung von Wasch- oder Reinigungsmitteln
EP2343359A1 (fr) * 2010-01-07 2011-07-13 Unilever PLC Formulation de détergent contenant des granules séchées par atomisation
RU2650892C2 (ru) * 2016-04-07 2018-04-18 Наталия Тимофеевна Тараненко Паста для стирки детского белья "Я МАМА"
EP3611247B1 (fr) * 2018-08-14 2021-03-10 The Procter & Gamble Company Compositions de traitement de tissus comprenant des capsules d'agent traitant

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EP0510746A2 (fr) * 1991-04-12 1992-10-28 The Procter & Gamble Company Procédé pour la préparation de granules de détergent condensés

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EP0510746A2 (fr) * 1991-04-12 1992-10-28 The Procter & Gamble Company Procédé pour la préparation de granules de détergent condensés

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DE69227311T2 (de) 1999-06-02
CN1243867A (zh) 2000-02-09
AU4642193A (en) 1994-02-14
MA22931A1 (fr) 1994-04-01
CN1083859A (zh) 1994-03-16
CA2140285C (fr) 1999-01-26
DE69227311D1 (de) 1998-11-19
DK0578872T3 (da) 1999-06-23
TR28449A (tr) 1996-07-04
IE930520A1 (en) 1994-01-26
CN1054631C (zh) 2000-07-19
CA2140285A1 (fr) 1994-02-03
EP0578872A1 (fr) 1994-01-19
WO1994002574A1 (fr) 1994-02-03
JP3560340B2 (ja) 2004-09-02
JPH07509268A (ja) 1995-10-12
CN1094512C (zh) 2002-11-20
ATE172240T1 (de) 1998-10-15
PH31248A (en) 1998-06-18
EG20369A (en) 1999-01-31
ES2121814T3 (es) 1998-12-16

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