EP0641381B1 - Procede de fabrication d'un detergent se presentant sous forme de pate - Google Patents

Procede de fabrication d'un detergent se presentant sous forme de pate Download PDF

Info

Publication number
EP0641381B1
EP0641381B1 EP93909938A EP93909938A EP0641381B1 EP 0641381 B1 EP0641381 B1 EP 0641381B1 EP 93909938 A EP93909938 A EP 93909938A EP 93909938 A EP93909938 A EP 93909938A EP 0641381 B1 EP0641381 B1 EP 0641381B1
Authority
EP
European Patent Office
Prior art keywords
soap
nonionic
anionic surfactants
incorporated
mixture
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
EP93909938A
Other languages
German (de)
English (en)
Other versions
EP0641381B2 (fr
EP0641381A1 (fr
Inventor
Hans-Josef Beaujean
Jens Bode
Norbert Schäfer
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6459194&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0641381(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0641381A1 publication Critical patent/EP0641381A1/fr
Application granted granted Critical
Publication of EP0641381B1 publication Critical patent/EP0641381B1/fr
Publication of EP0641381B2 publication Critical patent/EP0641381B2/fr
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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present patent application relates to a process for the preparation of pasty, anhydrous or low-water detergents and cleaning agents which, despite containing insoluble constituents, are stable to sedimentation.
  • Paste-like detergents and cleaning agents have advantages in terms of their ease of handling and in terms of their ease of manufacture on the apparatus side, a further advantage being that the formulation constituents have a relatively wide scope and thus the composition largely depends on specific washing technology Can customize needs.
  • pasty detergents differ from pourable detergents which, if no suitable measures are taken, have undesirable sedimentation if they contain insoluble constituents.
  • active oxygen compounds are part of the formulation, detergents of this type generally also have a breakdown of active oxygen which is not technically acceptable. This is favored by unbound water, by polyfunctional alcohols (preferably with neighboring OH groups or also with residual monomer components in polyols). Sedimentation-stable pasty detergents behave more favorably in this regard.
  • the object of the present invention was therefore to provide a process for the simple production of paste-like detergents which, despite a content of insoluble constituents, are stable to sedimentation.
  • An essential feature of the paste-like detergents to be produced is their low or no water.
  • the present invention relates to a process for the preparation of pasty, low-water or anhydrous detergents containing nonionic and anionic surfactants, soap, builders and bleaching agents, which are characterized in that the soap is incorporated in the heated mixture of nonionic and anionic surfactants in finely divided or dispersed form and, after this mixture has cooled, the other detergent components are incorporated.
  • low water means that no more than 3% by weight of water is added to the detergents during manufacture. In addition, water can be present in small amounts as a minor component of recipe components.
  • water-free means that no water is added to the detergents to be produced by the process according to the invention, but that water can be present in small amounts as a secondary component of formulation components.
  • Suitable anionic surfactants are, for example, synthetic surfactants of the sulfonate, sulfate or succinate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (C9- to C15-alkyl), mixtures of alkane and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration.
  • alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohols) and those of secondary alcohols.
  • the alkoxylation products of the aforementioned sulfate-type surfactants are also suitable.
  • Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols are also suitable.
  • Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids, such as. B. the fatty acid sarcosides, -glycolates, -lactates, -taurides or -isäthionate.
  • Anionic succinate-type surfactants are, for example, alkyl succinates with long-chain alkyl radicals or alkyl sulfosuccinates.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Nonionic surfactants are, for example, adducts of 4 to 40, preferably 4 to 20, moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide.
  • the addition products of 5 to 16 mol of ethylene oxide with coconut oil or tallow fatty alcohol, with oleyl alcohol or with secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals are particularly important.
  • non-or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • the water-soluble addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with ethylene oxide or propylene oxide, alkylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical can be used as nonionic surfactants.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • alkylene oxide with long-chain alcohols examples include mixtures of oleyl alcohol and cetyl alcohol with an iodine number in the range from 50 to 55, to which about 7 moles of ethylene oxide have been added per mole of alcohol, C12- to C18-fatty alcohol, to the about 5 moles of ethylene oxide have been added and C13 to C15 oxo alcohol to which 5 to 8 moles of ethylene oxide have been added.
  • Other interesting nonionic surfactants of this type are addition products of ethylene oxide and propylene oxide with fatty alcohols.
  • alkyl glucosides with a C8 to C18 alkyl radical, preferably with an alkyl radical consisting essentially of C10 to C16, which is derived from decyl, lauryl, myristyl, cetyl and stearyl alcohol and from technical Derives fractions that preferably contain saturated alcohols.
  • alkyl glucosides the alkyl radical of which contains 50 to 70% by weight of C12 and 18 to 30% by weight of C14 alkyl radicals.
  • the degree of oligomerization of suitable alkyl glucosides is between 1 and 10, preferably between 1 and 6.
  • soap is also an anionic surfactant, it is treated as a separate component in the present patent application.
  • Suitable soaps are the salts of saturated and unsaturated fatty acids with 12 to 18 carbon atoms, which can also be in the form of their mixtures.
  • Suitable builders are in particular zeolite A, polycarboxylates, citrate, phosphonates, carbonates, silicates, aminopolycarboxylic acid and polymers made from acrylic acid and maleic anhydride.
  • Suitable bleaching agents which emit hydrogen peroxide in the wash liquor are, for example, sodium perborate tetrahydrate (NaBO2 ⁇ H2O2 ⁇ 3 H2O) and monohydrate (NaBO2 ⁇ H2O2). But there are also other hydrogen peroxide-producing borates, for example the perborax (Na2B4O7 ⁇ H2O). These compounds can be partially or completely by other active oxygen carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na2CO3 ⁇ 1.5 H2O2), peroxypyrophosphates, citrate perhydrates, urea-H2O2- or melamine-H2O2 compounds as well as by hydrogen peroxide-providing peracid salts, such as.
  • insoluble stabilizers are alkaline earth metal silicates and water-soluble stabilizers are, for example, organic complexing agents.
  • detergents to be produced according to the invention are to be used at low washing temperatures, it is advisable to add activators. These cause the hydrogen peroxide to be released even at lower washing temperatures.
  • activators such as, for example, tetraacetylethylene diamine (TAED) or tetraacetylglycoluril (TAGU) are suitable.
  • the soap is incorporated either in finely divided or dispersed form.
  • finely divided means a particle size of less than 0.4 mm.
  • the soap can be worked in without the addition of water and without the use of powerful dispersants.
  • Another way of incorporating the soap is to incorporate the soap in dispersed form into the heated mixture of nonionic and anionic surfactants. It is preferred that the mixture of nonionic and anionic surfactants is heated to 70 to 90 ° C., preferably 80 to 85 ° C., before the soap is incorporated.
  • a further embodiment of the process according to the invention is characterized in that the soap is incorporated into the heated mixture of the nonionic and anionic surfactants in particle form with a particle size of at most 0.4 mm without the addition of water.
  • the incorporation of the soap is made easier in many cases by using powerful dispersants.
  • a further embodiment of the method according to the invention therefore consists in incorporating the soap into the heated mixture of the nonionic and anionic surfactants using a mixing unit which works according to the stator / rotor principle.
  • the amount of water used is preferably such that the finished detergent contains at most 1% by weight of water.
  • the mixture which now consists of anionic surfactants, nonionic surfactants and soap, has cooled, the remaining detergent components are incorporated.
  • the mixture of nonionic and anionic surfactants and soap is preferably cooled to below 30 ° C. before the other detergent components are incorporated.
  • a preferred embodiment of the process according to the invention is characterized in that at least two different nonionic surfactants are used in the mixture of nonionic and anionic surfactants.
  • These nonionic surfactants are preferably fatty alcohol ethoxylates with 12 to 18 carbon atoms in the fatty alcohol residue and with different degrees of ethoxylation in the range from 2 to 7 moles of ethylene oxide per mole of fatty alcohol, which are used in amounts of 3 to 60% by weight, based on the finished detergent.
  • the type and amount of soap used is important for adjusting the pasty consistency of the detergents produced according to the invention.
  • Sodium salts of linear fatty acids having 12 to 22 carbon atoms are preferably used as soap in amounts of 0.5 to 10% by weight, based on the finished detergent.
  • the paste-like consistency of the detergents is established in the course of 24 hours after the mixture has been mixed. Until then, the detergent produced according to the invention is pourable and can be easily conveyed, pumped and filled.
  • polycarboxylates and / or phosphonates and / or carbonates and / or silicates are preferably used as builders in amounts of 10 to 50% by weight, based on the finished detergent.
  • Another preferred builder is water-insoluble zeolite A.
  • sodium perborate and / or sodium percarbonate is preferably used as the bleaching agent, if desired in combination with activators, of which tetraacetylethylene diamine or diperoxydodecanedioic anhydride in addition to tetraacetylglycoluril in amounts of 10 to 30% by weight, based on the finished detergent, are preferred.
  • detergent components such as. B. Incorporate enzymes, foam inhibitors, optical brighteners, dirt carriers, fragrances and dyes in small quantities.
  • the advantages of the detergents produced according to the invention are that, with reliable sedimentation stability, the detergents are initially flowable and can be easily pumped, conveyed and filled in this state, and that after about 24 hours the paste-like consistency is established, which ensures the handling advantages described at the outset.
  • detergents produced according to the invention have a negligibly low breakdown of active oxygen.
  • a mixture of nonionic and anionic surfactants of the following composition was prepared at 80 to 85 ° C: 33.5% by weight C12-15 oxo alcohol + 2 moles of ethylene oxide 16.5% by weight C12-18 fatty alcohol + 7 moles of ethylene oxide 6.5% by weight C13-17 alkanesulfonate - sodium salt 6.5% by weight C12-16 alkyl sulfate - sodium salt 0.2% by weight C12-18 fatty acid - sodium salt.
  • the soap was incorporated as a dispersion in 1 part by weight of water.
  • the surfactant mixture thus obtained was mixed with 2.1% by weight 1-hydroxyethane-1,1-diphosphonic acid, disodium salt 5.5% by weight Copolymer of acrylic acid and maleic anhydride ("Sokalan CP 5" (R), company BASF, Germany) 10.0% by weight Sodium perborate monohydrate 3.0% by weight Tetraacetylethylenediamine 5.5% by weight Zeolite A 8.1% by weight sodium Rest up to 100% in total optical brightener, foam regulator, fragrance, enzyme in small quantities.
  • the mixture was liquid and was easy to pump, pump and fill.
  • the sodium perborate monohydrate had the following particle size distribution: > 1.0 mm 0.1% > 0.5 mm 14.7% > 0.4 mm 37.4% > 0.2 mm 90.7% > 0.1 mm 99.99%.
  • the sodium carbonate was 60.7% with a grain size of> 0.1 mm.

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (11)

  1. Procédé de préparation de produits de lavage en pâte, sans eau ou pauvres en eau ayant une teneur en tensioactifs non ioniques et anioniques, savons, substances de structure et agents de blanchiment, caractérisé en ce qu'on incorpore le savon dans le mélange chauffé des tensioactifs non ioniques et anioniques sous forme finement divisée ou dispersée, et après refroidissement de ce mélange, on incorpore les autres composants du produit de lavage.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on chauffe les tensioactifs non ionique et anioniques avant l'incorporation du savon entre 70 et 90, de préférence entre 80 et 85°C.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on incorpore le savon sous forme de particules ayant une taille de particules ne dépassant pas 0,4 mm sans addition d'eau dans le mélange chauffé des tensioactifs non ioniques et anioniques.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on incorpore le savon en utilisant un appareil de mélange, qui fonctionne selon le principe Stator-Rotor, dans le mélange chauffé des tensioactifs non ioniques et anioniques.
  5. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'on disperse le savon avant l'incorporation dans suffisamment d'eau pour que le produit de lavage terminé contienne au plus 1 % en poids d'eau.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce qu'on incorpore les autres composants du produit de lavage après le refroidissement du mélange de tensioactifs non ioniques et anioniques ainsi que le savon en dessous de 30°C.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on utilise dans le mélange de tensioactifs non ioniques et anioniques au moins deux tensioactifs non ioniques différents, de préférence des éthoxylates d'alcool gras de 12 à 18 atomes de carbone dans le radical alcool gras et de taux d'éthoxylation différents dans l'intervalle de 2 à 7 mol d'oxyde d'éthylène par mol d'alcool gras en des quantités de 3 à 60 % en poids, par rapport au produit de lavage terminé.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'on utilise comme savon des sels de sodium d'acides gras linéaires de 12 à 22 atomes de carbone en des quantités de 0,5 à 10 % en poids, par rapport au produit de lavage terminé.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce qu'on utilise comme substances de structure des polycarboxylates et/ou des phosphonates et/ou des carbonates et/ou des silicates en des quantités de 10 à 50 % en poids par rapport au produit de lavage terminé.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce qu'on utilise comme agent blanchissant du perborate de sodium et/ou du percarbonate de sodium, si c'est souhaité en combinaison avec des activateurs comme par exemple notamment la tétraacétyléthylènediamine ou l'anhydride d'acide diperoxydodécanedioïque en des quantités de 10 à 30 % en poids par rapport au produit de lavage terminé.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on incorpore d'autres composants de produit de lavage, comme par exemple des enzymes, des inhibiteurs de mousse, des azurants optiques, des agents d'antiredéposition, des parfums et colorants en faibles quantités.
EP93909938A 1992-05-19 1993-05-11 Procede de fabrication d'un detergent se presentant sous forme de pate Expired - Lifetime EP0641381B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4216453 1992-05-19
DE4216453A DE4216453A1 (de) 1992-05-19 1992-05-19 Verfahren zur Herstellung pastenförmiger Waschmittel
PCT/EP1993/001146 WO1993023521A1 (fr) 1992-05-19 1993-05-11 Procede de fabrication d'un detergent se presentant sous forme de pate

Publications (3)

Publication Number Publication Date
EP0641381A1 EP0641381A1 (fr) 1995-03-08
EP0641381B1 true EP0641381B1 (fr) 1996-02-21
EP0641381B2 EP0641381B2 (fr) 1999-09-29

Family

ID=6459194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93909938A Expired - Lifetime EP0641381B2 (fr) 1992-05-19 1993-05-11 Procede de fabrication d'un detergent se presentant sous forme de pate

Country Status (13)

Country Link
US (1) US5518645A (fr)
EP (1) EP0641381B2 (fr)
JP (1) JPH07506607A (fr)
KR (1) KR950701679A (fr)
AT (1) ATE134384T1 (fr)
CA (1) CA2136173A1 (fr)
DE (2) DE4216453A1 (fr)
DK (1) DK0641381T4 (fr)
ES (1) ES2083285T5 (fr)
FI (1) FI945417A0 (fr)
GR (2) GR3019219T3 (fr)
NO (1) NO306560B1 (fr)
WO (1) WO1993023521A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6916596B2 (en) 1993-06-25 2005-07-12 Michael Wen-Chein Yang Laser imaged printing plates
US6756181B2 (en) 1993-06-25 2004-06-29 Polyfibron Technologies, Inc. Laser imaged printing plates
US5506201A (en) * 1994-04-29 1996-04-09 International Flavors & Fragrances Inc. Formulation of a fat surfactant vehicle containing a fragrance
DE4436151A1 (de) * 1994-08-16 1996-05-02 Henkel Kgaa Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
BR9509082A (pt) * 1994-09-26 1998-06-23 Procter & Gamble Composiçoes detergentes líquidas contendo alvejante n o-aquosas
AU3584195A (en) * 1994-09-26 1996-04-19 Procter & Gamble Company, The Process for preparing non-aqueous, bleach-containing liquid detergent compositions
DE19535082A1 (de) 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US6083488A (en) * 1996-12-04 2000-07-04 The Block Drug Company Barrier to plaque formation
DE19703364A1 (de) * 1997-01-30 1998-08-06 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US5863887A (en) * 1997-12-01 1999-01-26 Precision Fabrics Group, Inc. Laundry compositions having antistatic and fabric softening properties, and laundry detergent sheets containing the same
US6130193A (en) * 1998-02-06 2000-10-10 Precision Fabrics Group, Inc. Laundry detergent compositions containing silica for laundry detergent sheets
DE10017540C2 (de) * 2000-04-08 2002-07-04 Henkel Kgaa Verfahren zur Herstellung von flüssigen bis gelförmigen Reinigungsmitteln
US7694583B2 (en) * 2005-05-05 2010-04-13 Control Gaging, Inc. Gripper gage assembly
JP5868747B2 (ja) * 2012-03-19 2016-02-24 花王株式会社 界面活性剤混合物の製造方法
DE102012015826A1 (de) 2012-08-09 2014-02-13 Clariant International Ltd. Flüssige tensidhaltige Alkanolamin-freie Zusammensetzungen
DE102017208559A1 (de) * 2017-05-19 2018-11-22 Henkel Ag & Co. Kgaa Verfahren zur Herstellung gelförmiger Substanzen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8522621D0 (en) * 1985-09-12 1985-10-16 Unilever Plc Detergent powder
DE3621536A1 (de) * 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
DE3842007A1 (de) * 1988-12-14 1990-06-21 Henkel Kgaa Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
DE3914504A1 (de) * 1989-05-02 1990-11-08 Henkel Kgaa Pastoeses, phosphatfreies, im wesentlichen wasserfreies waschmittel
GB2237285A (en) * 1989-10-27 1991-05-01 Unilever Plc Liquid soap composition
DE4009532A1 (de) * 1990-03-24 1991-09-26 Henkel Kgaa Waschmittel-formkoerper
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability

Also Published As

Publication number Publication date
FI945417A (fi) 1994-11-17
ES2083285T3 (es) 1996-04-01
EP0641381B2 (fr) 1999-09-29
ES2083285T5 (es) 1999-11-16
NO306560B1 (no) 1999-11-22
GR3019219T3 (en) 1996-06-30
DK0641381T4 (da) 2000-01-03
NO943320D0 (no) 1994-09-08
JPH07506607A (ja) 1995-07-20
EP0641381A1 (fr) 1995-03-08
FI945417A0 (fi) 1994-11-17
DE4216453A1 (de) 1993-11-25
ATE134384T1 (de) 1996-03-15
NO943320L (no) 1994-09-08
DK0641381T3 (da) 1996-06-24
CA2136173A1 (fr) 1993-11-25
GR3031777T3 (en) 2000-02-29
KR950701679A (ko) 1995-04-28
US5518645A (en) 1996-05-21
WO1993023521A1 (fr) 1993-11-25
DE59301689D1 (de) 1996-03-28

Similar Documents

Publication Publication Date Title
EP0641381B1 (fr) Procede de fabrication d'un detergent se presentant sous forme de pate
DE68926228T2 (de) Waschmittelzusammensetzung
EP0253151A2 (fr) Agent de lavage liquide et procédé pour sa production
DE69018676T2 (de) Flüssige Detergensprodukte.
EP0201016A2 (fr) Détergents liquides exempts de renforçateurs ayant des propriétés adoucissantes pour matières textiles
DE69706172T3 (de) Nichtwässrige waschmittelzusammensetzungen enthaltend spezifisches alkylbenzolsulfonattensid
DE4436151A1 (de) Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
DE3842007A1 (de) Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
JPS62186930A (ja) エステルスルホネ−ト含有界面活性剤濃厚液およびその用途
DE3022767A1 (de) Waessrig-fluessiges, builderhaltiges waschmittel
DE3904610A1 (de) Waschmittel fuer waschkraftverstaerker
EP0131137A1 (fr) Agent de lavage et de nettoyage avec une teneur en sels d'acylcyanamide
DE102005039971A1 (de) Flüssigwaschmittelformulierung
EP0079105B1 (fr) Agents de lavage à mousse contrôlée
EP1217064B1 (fr) Agents tensio-actifs non-ioniques
EP0576479B1 (fr) Produit de lavage liquide ou pateux
EP1080175A1 (fr) Agent de blanchiment aqueux
EP0609303B1 (fr) Detergent liquide concentre pour surfaces dures
EP0647261B1 (fr) Granule de lavage et de nettoyage
CH676604A5 (fr)
EP0647260B1 (fr) Agents de lavage et de nettoyage se presentant sous forme liquide a pateuse
EP0157320B1 (fr) Lessive pour lavage à froid à la main et en machine
DE3905671C2 (de) Zur Herstellung wäßriger Konzentrate geeignetes Waschmittelgranulat
DE4228043A1 (de) Gerüststoff für Waschmittel
DE4428958A1 (de) Flüssigwaschmittel mit Bleiche

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

17P Request for examination filed

Effective date: 19941111

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19950316

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 FR GB GR IE IT LI NL SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960221

REF Corresponds to:

Ref document number: 134384

Country of ref document: AT

Date of ref document: 19960315

Kind code of ref document: T

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: 67315

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59301689

Country of ref document: DE

Date of ref document: 19960328

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2083285

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960426

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3019219

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V.

Effective date: 19961121

NLR1 Nl: opposition has been filed with the epo

Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19990929

AK Designated contracting states

Kind code of ref document: B2

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

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

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19991108

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 19991013

ET3 Fr: translation filed ** decision concerning opposition
NLR2 Nl: decision of opposition
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: DK

Ref legal event code: T4

NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
GBTA Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977)

Effective date: 20000128

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

Ref country code: ES

Payment date: 20000531

Year of fee payment: 8

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

Ref country code: SE

Payment date: 20010417

Year of fee payment: 9

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

Ref country code: DE

Payment date: 20010508

Year of fee payment: 9

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

Ref country code: GB

Payment date: 20010509

Year of fee payment: 9

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

Ref country code: CH

Payment date: 20010511

Year of fee payment: 9

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

Ref country code: DK

Payment date: 20010514

Year of fee payment: 9

Ref country code: AT

Payment date: 20010514

Year of fee payment: 9

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

Ref country code: FR

Payment date: 20010518

Year of fee payment: 9

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

Ref country code: IE

Payment date: 20010528

Year of fee payment: 9

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

Ref country code: GR

Payment date: 20010530

Year of fee payment: 9

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

Ref country code: NL

Payment date: 20010531

Year of fee payment: 9

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

Ref country code: BE

Payment date: 20010717

Year of fee payment: 9

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: AT

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

Effective date: 20020511

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 NON-PAYMENT OF DUE FEES

Effective date: 20020512

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: 20020513

Ref country code: ES

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

Effective date: 20020513

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

Ref country code: LI

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

Effective date: 20020531

Ref country code: DK

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

Effective date: 20020531

Ref country code: CH

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

Effective date: 20020531

Ref country code: BE

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

Effective date: 20020531

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 NON-PAYMENT OF DUE FEES

Effective date: 20021201

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: 20021203

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

Effective date: 20020511

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20030131

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

Effective date: 20021201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030611

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

Ref country code: IT

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

Effective date: 20050511