[go: up one dir, main page]

EP0816486B1 - Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate - Google Patents

Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate Download PDF

Info

Publication number
EP0816486B1
EP0816486B1 EP96201855A EP96201855A EP0816486B1 EP 0816486 B1 EP0816486 B1 EP 0816486B1 EP 96201855 A EP96201855 A EP 96201855A EP 96201855 A EP96201855 A EP 96201855A EP 0816486 B1 EP0816486 B1 EP 0816486B1
Authority
EP
European Patent Office
Prior art keywords
paste
surfactant
alkyl
process according
weight
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
EP96201855A
Other languages
English (en)
French (fr)
Other versions
EP0816486A1 (de
Inventor
Lucas Goovaerts
Liben Hailu
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
Priority to AT96201855T priority Critical patent/ATE264384T1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69632187T priority patent/DE69632187T2/de
Priority to EP96201855A priority patent/EP0816486B1/de
Priority to AU36442/97A priority patent/AU3644297A/en
Priority to CA002260008A priority patent/CA2260008C/en
Priority to US09/214,328 priority patent/US6172033B1/en
Priority to JP10505242A priority patent/JPH11514034A/ja
Priority to BR9710197A priority patent/BR9710197A/pt
Priority to PCT/US1997/011282 priority patent/WO1998001529A1/en
Priority to CN97197366.0A priority patent/CN1228115A/zh
Priority to ARP970102993A priority patent/AR008771A1/es
Publication of EP0816486A1 publication Critical patent/EP0816486A1/de
Application granted granted Critical
Publication of EP0816486B1 publication Critical patent/EP0816486B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D1/02—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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a process for making a granular detergent component or composition.
  • granular detergent products are made by forming a neutral or alkaline paste comprising at least 40% by weight of anionic surfactant; and mixing the high viscosity paste so-formed with builder powders wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5 to form the granular detergent component or composition.
  • Such processes are commonly called agglomeration processes
  • EP-A-0,663,439 and EP-A-0,508,543 both describe enhanced embodiments of agglomeration processes which includes a process of surfactant paste conditioning in, for example, a twin-screw extruder, followed by granulation in a high shear mixer.
  • EP-A-0,508,543 mentions the possibility to add anionic surfactant into the process via a powder stream. However it is not specified whether this powder stream is added into the extruder, or into the high-shear mixer. Neither of these publications describes the use of dry alkyl sulphate powder in the conditioning step.
  • an anionic surfactant paste is formed and alkyl ethoxy sulphate is added to it, the alkyl ethoxy sulphate preferably being added directly to a neutralisation loop by which the anionic surfactant is made or as a result of the ethoxylated alcohol being sulphated at the same time as the sulphation or sulphonation of the anionic surfactant followed by neutralisation of both.
  • WO93/25378 a process is described in which the builder powders which are used for the agglomeration may include powdered anionic surfactant and it is also mentioned that the liquid stream into the agglomeration process can be used to introduce other surfactants and/or polymers.
  • the examples do not illustrate these variations.
  • the object of the present invention is to provide an effective process for conditioning pastes comprising at least 40% by weight of anionic surfactant.
  • the conditioning agent disrupts surfactant crystallinity, and also increases the viscoelasticity of the paste.
  • the crystalline disruption improves rate of surfactant solubility, whilst the viscoelasticity increase "conditions" the paste enabling agglomerates with high surfactant activity to be formed.
  • a process according to the invention for making a granular detergent component or composition comprises the steps of forming a conditioned, high viscosity, neutral or alkaline surfactant paste comprising more than 40% by weight of anionic surfactant, and forming the granular detergent component or composition by mixing the conditioned high viscosity paste with builder powders in mixer/agglomerator apparatus, wherein the ratio of high viscosity paste to builder powder is from 9:1 to 1:5, and in this process the conditioned high viscosity paste is made by forming an aqueous neutral or alkaline surfactant paste comprising at least 40% by weight of anionic surfactant and then conditioning the paste by mixing into the paste at least one part by weight alkyl sulphate powder per 100 parts by weight paste and thereby increasing the viscosity of the paste.
  • the alkyl sulphate powder preferably comprises at least 80% by weight alkyl sulphate and preferably comprises less than 5% by weight water.
  • aqueous neutral or alkaline surfactant paste is mixed into the previously formed aqueous neutral or alkaline surfactant paste in an extruder.
  • the builder powders are preferably selected from carbonate, aluminosilicate and silicate.
  • the mixer/agglomerator apparatus which is used for forming the granular detergent component by mixing the paste with the powders preferably comprises a high shear mixer granulator having a tool tip-speed of from 5 to 50 m/sec followed in sequence by a medium speed agglomerator.
  • the process accordingly relates to conditioning an aqueous, highly concentrated, solution of a salt, usually the sodium salt, of anionic surfactant and which is a high active paste.
  • a salt usually the sodium salt
  • anionic surfactant pastes are of a high viscosity but remain pumpable at temperatures at which the surfactants are stable.
  • anionic surfactants or mixtures comprising at least one anionic surfactant, where highly viscous liquid crystal phases occur requires that either lower viscous crystal phases be formed or that some viscosity modifiers are used. This requires expensive additives, and prevents high surfactant activities from being achieved.
  • Conditioning of a paste means the modifying of its physical characteristics to form higher active, less sticky agglomerates which are not easily obtainable under normal operating conditions.
  • Conditioning of the paste as defined herein means: a) increasing its apparent viscosity, b) increasing its effective melting point, c) increasing the "hardness" of the paste.
  • the hardness/softness of the paste may be measured by a softness penetrometer according to ASTM D 217-IP50 or ISO 2137.
  • the hardness of conditioned paste measured in this way should be less than 2cm, preferably less than 1cm.
  • Chemical conditioning agents are compounds that alter the physical structure and/or physical characteristics of the surfactant paste when added to the paste.
  • the chemical conditioning agent is alkyl sulphate in powdered form. It has been found that the addition to the surfactant paste reduces the stickiness of the paste, increases its viscosity and increases its softening point. This allows for more paste to be added during the agglomeration process thus leading to higher active agglomerates, preferably between 40% and 60%, more preferably greater than 50%.
  • This method of treating the surfactant paste can be performed batchwise and continuous, preferably continuously.
  • Alkyl sulphate powder is defined herein as any free-flowing powder, flakes, noodles or needles which comprises at least 80% by weight of alkyl sulphate.
  • Useful powders are commercially available from Albright & Wilson, Hickson Manro and Sidobre Sinnova.
  • suitable powders may be prepared by sulphating an alcohol, followed by neutralisation with, for example aqueous sodium hydroxide, then drying in a suitable spray drying tower, wiped film evaporator or suitable dryer. Dry neutralisation methods may also be used, neutralising alkyl sulphuric acid with, for example powdered sodium carbonate.
  • an extruder is used to condition the paste.
  • the extruder is a versatile piece of equipment which enables two or more pastes and the alkyl sulphate powder to be mixed
  • Process aids may also be used.
  • Preferred process aids which may be mixed with the surfactant paste are starch, soap, fatty acids and polymers.
  • Process aids and surfactant paste may be mixed prior to the extruder in, for example, a high shear mixer; or in the extruder itself.
  • 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 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%.
  • 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 about 5,000 cps to 10,000,000 cps.
  • the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps.
  • the viscosity of the paste of this invention is measured at a temperature of 70°C.
  • 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.
  • 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 : 50-80% and 65-75%.
  • the balance of the paste is primarily water but can include a processing aid such as a nonionic surfactant.
  • the resultant concentrated surfactant granules are added to dry builder powders 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 and are not included herein as an "active" surfactant.
  • cationic 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 about 10 to about 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 about 9 to about 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 about 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 about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
  • the acid salts are typically discussed and used, the
  • 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 about 0.01:1 to about 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 about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • 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 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 25 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 about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 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 about 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 about 8 to 18 carbon atoms.
  • Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 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 about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 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
  • Useful cationic surfactants include.
  • 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.
  • Specific preferred surfactants for use herein include: sodium linear C 11 -C 13 alkylbenzene sulfonate; ⁇ -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 to 19:1, preferably from 0.05 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 extruder fulfils the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
  • a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel.
  • the detailed design of the extruder allows various functions to be carried out. Firstly additional ports in the barrel may allow other ingredients, including the alkyl sulphate powder to be added directly into the barrel. Secondly means for heating or cooling may be installed in the wall of the barrel for temperature control. Thirdly, careful design of the extruder screw promotes mixing of the paste both with itself and with other additives.
  • a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation).
  • the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
  • Suitable twin screw extruders for use in the present invention include those supplied by : APV Bakes, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
  • fine dispersion mixing and granulation means mixing and granulation of the above mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 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 about 10-45 m/sec. and about 15-40 m/sec.
  • Suitable apparatus for forming the initial paste includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
  • Suitable apparatus for mixing/agglomeration 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 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 inlcude 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., Bershire, 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 100°C, more preferably between 25 and 90°C, and most preferably between 30 and 80°C.
  • 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 from about 0.4 to about 1.2 g/cc, more preferably from about 0.6 to about 0.8 g/cc.
  • the weight average particle size of the particles of this invention are from about 200 to about 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 about 25°C to about 60°C, and most preferably from about 30°C to about 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 2-4%.
  • 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 about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 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 about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 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 about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 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 about 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 about 300 mg eq./g to about 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of . from about 2 grains/gallon/minute/gram/gallon to about 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 about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least about 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 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, Zeolite X and Zeolite P.
  • the crystalline aluminosilicate ion exchange material has the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 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 polyhyroxysulfonates.
  • 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 about 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 about 0.5 to about 4.0, preferably from about 1.0 to about 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, perborate, etc. and process aids such as starch, soap or fatty acid 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 polycarboxyate 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, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents, perfumes, soap and fatty acid.
  • flow aids include color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents, perfumes, soap and fatty acid.
  • the AE3S/AS paste, and the LAS paste when present were fed into a continuous twin-screw extruder.
  • the alkyl sulphate powder, or the polyacrylate polymer, and silicate when present, were added directly to into the barrel of the extruder through an inlet port.
  • the mixture was then extruded through a die directly into a high shear mixer (Loedige® CB) where is mixed with powder streams comprising the sodium carbonate and the zeolite.
  • the resulting product was then passed to a medium shear mixer (Loedige® KM) resulting in a free-flowing detergent product in the form of agglomerates.
  • AS/NI paste is a 95% aqueous solution of alkyl sulphate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of alkyl sulphate to 1 part of alcohol ethoxylate.
  • LAS/NI paste is a 95% active aqueous solution of sodium linear alkyl benzene sulphonate and alcohol ethoxylate (with 3 EO groups per molecule) comprising 2 parts of LAS to 1 part of alcohol ethoxylate.
  • the AS/NI paste, or the LAS/NI paste was fed into a continuous twin-screw extruder.
  • the alkyl sulphate powder was added directly to into the barrel of the extruder through an inlet port.
  • the mixture was then extruded through a die directly into a high shear mixer (Loedige® CB) where is mixed with powder streams comprising the sodium citrate and the zeolite.
  • the resulting product was then passed to a medium shear mixer (Loedige® KM) resulting in a free-flowing detergent product in the form of agglomerates.
  • the bulk density of the product from each of the examples was between 680 and 700 g/l.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (8)

  1. Verfahren zur Herstellung einer granulären Detergenskomponente oder - zusammensetzung, umfassend die Schritte des Bildens einer konditionierten, hochviskosen, neutralen oder alkalischen Tensidpaste, umfassend 40 oder mehr Gew.-% anionisches Tensid; und des Bildens der granulären Detergenskomponente oder -zusammensetzung durch Mischen der konditionierten hochviskosen Paste mit Builderpulvern in einer Mischer/Agglomerator-Vorrichtung, wobei das Verhältnis von hochviskoser Paste zu Builderpulver 9:1 bis 1:5 beträgt, dadurch gekennzeichnet, dass die konditionierte, hochviskose Paste hergestellt wird durch Bilden einer wässrigen, neutralen oder alkalischen Tensidpaste, umfassend mindestens 40 Gew.-% anionisches Tensid, und danach Konditionieren der Paste durch Einmischen in die Paste mindestens eines Gewichtsteils Alkylsulfatpulver pro 100 Gewichtsteile Paste und dadurch Erhöhen der Viskosität der Paste.
  2. Verfahren nach Anspruch 1, wobei das Alkylsulfatpulver weniger als 5 Gew.-% Wasser umfasst.
  3. Verfahren nach Anspruch 1, wobei die granuläre Detergenskomponente oder -zusammensetzung eine Schüttdichte von mindestens 0,6 g/cm3 besitzt und anionisches Tensid in einem Anteil zwischen 40 und 60 Gew.-% der Komponente oder der Zusammensetzung umfasst.
  4. Verfahren nach Anspruch 1, wobei das Builderpulver im Wesentlichen besteht aus Buildern, gewählt aus der Gruppe, bestehend aus Carbonat, Aluminosilicat, Silicat und Mischungen hiervon.
  5. Verfahren nach mindestens einem vorangehenden Anspruch, wobei die konditionierte Paste eine Prozesshilfe beinhaltet, gewählt aus Stärke, Seife, Fettsäure und Polymer, und welche in die konditionierte Paste vor oder mit dem Alkylsulfatpulver eingebracht wird.
  6. Verfahren nach mindestens einem vorangehenden Anspruch, wobei das Alkylsulfatpulver in die wässrige Tensidpaste in einem Extruder eingemischt wird.
  7. Verfahren nach mindestens einem vorangehenden Anspruch, wobei die Mischer/Agglomerator-Vorrichtung aufeinanderfolgend einen Hochschermischer-Granulator mit einer Werkzeugspitzengeschwindigkeit von 5 bis 50 m/s und einen Mäßiggeschwindigkeits-Agglomerator umfasst.
  8. Verfahren nach mindestens einem vorangehenden Anspruch, wobei die konditionierte, hochviskose Paste eine viskoelastische Paste mit einer Viskosität bei 70°C von 20.000 cps bis 100.000 cps ist.
EP96201855A 1996-07-04 1996-07-04 Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate Expired - Lifetime EP0816486B1 (de)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE69632187T DE69632187T2 (de) 1996-07-04 1996-07-04 Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate
EP96201855A EP0816486B1 (de) 1996-07-04 1996-07-04 Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate
AT96201855T ATE264384T1 (de) 1996-07-04 1996-07-04 Verfahren zur konditionierung von tensidpasten zwecks bildung hochaktiver tensidgranulate
CA002260008A CA2260008C (en) 1996-07-04 1997-06-27 Process for conditioning of surfactant pastes to form high active surfactant agglomerates
US09/214,328 US6172033B1 (en) 1996-07-04 1997-06-27 Process for conditioning of surfactant pastes to form high active surfactant agglomerates
JP10505242A JPH11514034A (ja) 1996-07-04 1997-06-27 界面活性剤ペーストをコンディショニングして高い活性の界面活性剤凝集物を形成させる方法
AU36442/97A AU3644297A (en) 1996-07-04 1997-06-27 Process for conditioning of surfactant pastes to form high active surfactant agglomerates
BR9710197A BR9710197A (pt) 1996-07-04 1997-06-27 Processo para o condicionamento de pastas de tensoativo para constituir aglomerados de tensoativo altamente ativo
PCT/US1997/011282 WO1998001529A1 (en) 1996-07-04 1997-06-27 Process for conditioning of surfactant pastes to form high active surfactant agglomerates
CN97197366.0A CN1228115A (zh) 1996-07-04 1997-06-27 调节表面活性剂浆料以形成高活性表面活性剂附聚物的方法
ARP970102993A AR008771A1 (es) 1996-07-04 1997-07-03 Proceso para la fabricacion de un componente detergente o composicion granulada, acondicionando pastas surfactantes para formar aglomerados de altaactividad

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96201855A EP0816486B1 (de) 1996-07-04 1996-07-04 Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate

Publications (2)

Publication Number Publication Date
EP0816486A1 EP0816486A1 (de) 1998-01-07
EP0816486B1 true EP0816486B1 (de) 2004-04-14

Family

ID=8224141

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96201855A Expired - Lifetime EP0816486B1 (de) 1996-07-04 1996-07-04 Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate

Country Status (10)

Country Link
EP (1) EP0816486B1 (de)
JP (1) JPH11514034A (de)
CN (1) CN1228115A (de)
AR (1) AR008771A1 (de)
AT (1) ATE264384T1 (de)
AU (1) AU3644297A (de)
BR (1) BR9710197A (de)
CA (1) CA2260008C (de)
DE (1) DE69632187T2 (de)
WO (1) WO1998001529A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6172033B1 (en) 1996-07-04 2001-01-09 The Procter & Gamble Company Process for conditioning of surfactant pastes to form high active surfactant agglomerates
DE19722767A1 (de) * 1997-06-02 1998-12-03 Henkel Kgaa Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung
DE19911570A1 (de) * 1999-03-16 2000-09-28 Henkel Kgaa Aniontensid-Granulate
US7485615B2 (en) 2003-08-06 2009-02-03 Kao Corporation Process for producing granular anionic surfactant
JP4319133B2 (ja) * 2003-12-26 2009-08-26 花王株式会社 粒状アニオン界面活性剤の製造方法
CN1883784B (zh) * 2005-06-21 2010-10-13 花王株式会社 粒状阴离子表面活性剂的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1337513C (en) * 1988-07-21 1995-11-07 Michael William Hollingsworth Detergent compositions and process for preparing them
ES2104809T3 (es) * 1991-04-12 1997-10-16 Procter & Gamble Estructuracion quimica de pastas tensioactivas para formar granulos tensioactivos muy activos.
US5494599A (en) * 1991-04-12 1996-02-27 The Procter & Gamble Company Agglomeration of high active pastes to form surfactant granules useful in detergent compositions
DE4203031A1 (de) * 1992-02-04 1993-08-05 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
US5529722A (en) * 1992-03-10 1996-06-25 The Procter & Gamble Company High active detergent pastes
DE69229218T2 (de) * 1992-03-10 1999-12-16 The Procter & Gamble Co., Cincinnati Hochaktive Tensidpasten
EP0656825B2 (de) * 1992-06-15 2005-12-14 The Procter & Gamble Company Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
US5529710A (en) * 1992-07-15 1996-06-25 The Procter & Gamble Company Production of detergent granules with excellent white appearance
US5516448A (en) * 1994-09-20 1996-05-14 The Procter & Gamble Company Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate

Also Published As

Publication number Publication date
AR008771A1 (es) 2000-02-23
CA2260008C (en) 2002-05-21
JPH11514034A (ja) 1999-11-30
EP0816486A1 (de) 1998-01-07
CN1228115A (zh) 1999-09-08
DE69632187T2 (de) 2005-03-17
AU3644297A (en) 1998-02-02
CA2260008A1 (en) 1998-01-15
DE69632187D1 (de) 2004-05-19
BR9710197A (pt) 1999-08-10
ATE264384T1 (de) 2004-04-15
WO1998001529A1 (en) 1998-01-15

Similar Documents

Publication Publication Date Title
CA2108166C (en) Chemical structuring of surfactant pastes to form high active surfactantgranules
EP0656825B2 (de) Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
EP0510746A2 (de) Verfahren zur Herstellung verdichteter Reinigungsmittelgranulate
US5712242A (en) High active granular detergents comprising chelants and polymers, and processes for their preparation
US5663136A (en) Process for making compact detergent compositions
EP0578871B1 (de) Verfahren zur Herstellung von kompakten Reinigungsmitteln
US5494599A (en) Agglomeration of high active pastes to form surfactant granules useful in detergent compositions
US5529710A (en) Production of detergent granules with excellent white appearance
CA2140285C (en) Detergent compositions
US5451354A (en) Chemical structuring of surfactant pastes to form high active surfactant granules
EP0639638A1 (de) Verfahren zur Herstellung von Reinigungsmittelzusammensetzungen
EP0618289B1 (de) Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung
US5529722A (en) High active detergent pastes
US5703037A (en) Process for the manufacture of free-flowing detergent granules
EP0816486B1 (de) Verfahren zur Konditionierung von Tensidpasten zwecks Bildung hochaktiver Tensidgranulate
US6172033B1 (en) Process for conditioning of surfactant pastes to form high active surfactant agglomerates
EP0678573B1 (de) Verfahren zur Herstellung von rieselfähigen Waschmittelgranulaten
AU1878592A (en) Agglomeration of high active pastes to form surfactant granules useful in detergent compositions

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19980706

AKX Designation fees paid

Free format text: AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 20010515

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69632187

Country of ref document: DE

Date of ref document: 20040519

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040704

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

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040705

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040725

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050117

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: GB

Payment date: 20060614

Year of fee payment: 11

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

Ref country code: FR

Payment date: 20060705

Year of fee payment: 11

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

Ref country code: DE

Payment date: 20060731

Year of fee payment: 11

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

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040914

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070704

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080201

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070704

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20080331

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

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070731