EP2773736B1 - Produit de lavage ou de nettoyage structuré à limite d'écoulement - Google Patents

Produit de lavage ou de nettoyage structuré à limite d'écoulement Download PDF

Info

Publication number
EP2773736B1
EP2773736B1 EP12773309.5A EP12773309A EP2773736B1 EP 2773736 B1 EP2773736 B1 EP 2773736B1 EP 12773309 A EP12773309 A EP 12773309A EP 2773736 B1 EP2773736 B1 EP 2773736B1
Authority
EP
European Patent Office
Prior art keywords
cleaning agent
alcohols
washing
surfactant
mixtures
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.)
Revoked
Application number
EP12773309.5A
Other languages
German (de)
English (en)
Other versions
EP2773736A1 (fr
Inventor
Peter Schmiedel
Luca Bellomi
Aleidatje Martinetta Lester
Martina Hutmacher
Ines Baranski
Hendrik Hellmuth
Timothy O´CONNELL
Thomas Weber
Nadine Langenscheidt-Dabringhausen
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=47040718&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2773736(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE201110085638 external-priority patent/DE102011085638A1/de
Priority claimed from DE201210201980 external-priority patent/DE102012201980A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2773736A1 publication Critical patent/EP2773736A1/fr
Application granted granted Critical
Publication of EP2773736B1 publication Critical patent/EP2773736B1/fr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/655—Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/14—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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/667—Neutral esters, e.g. sorbitan 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear

Definitions

  • the invention relates to a liquid washing or cleaning agent with yield point, containing anionic and nonionic surfactant.
  • the invention also relates to the use of the washing or cleaning agent and a process for its preparation.
  • Stable suspension of solids in liquids is often problematic.
  • the solids differ in density from the liquid, they tend to sediment or float.
  • structured surfactant system refers to aqueous systems which have surfactant structures that are larger than conventional spherical micelles and whose interaction confers thixotropic properties on the aqueous medium. These structures may be solid, mesophase, or liquid, and may be in the form of multilayer spherulites, rods, discs, or lamellae that are dispersed or emulsified discontinuously in the system, or which form weak network structures.
  • L ⁇ phase in which bilayers of surfactants with the hydrophobic part of the molecule on the inside and the hydrophilic part on the outside of the bilayer (or vice versa) are located.
  • the bilayers lie side by side, for example in a parallel or concentric arrangement, sometimes separated by aqueous layers.
  • L ⁇ phases can usually be identified by their characteristic texture under the polarizing microscope and / or by X-ray diffraction.
  • L ⁇ phase usually can not be used as structured suspending systems. Useful amounts of solids cause the systems to become non-pourable and smaller amounts of solids tend to sediment. Also, the concentrations at which L ⁇ phases often occur are significantly higher than the usual and / or desired concentrations in liquid detergents and cleaners.
  • the main types of structured system used in practice are based on dispersed lamellar, spherulitic and attenuated lamellar phases.
  • Dispersed lamellar phases are two-phase systems in which the surfactant bilayers are arranged as parallel plates to form areas of La phases interspersed with an aqueous phase to form an opaque gel-like system.
  • Spherolitic phases include spherical bodies, commonly referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells.
  • the spherulites usually have a diameter in the range of 0.1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion.
  • the spherulites interact to form a structured system.
  • surfactant systems are dispersed between lamellar and spherulitic.
  • the surfactant systems include both types of structures. Usually systems of a more spherulitic character are preferred because they lead to lower viscosities.
  • a third type of structured surfactant system comprises an extended L ⁇ phase. It differs from the other two structural system types in that it is essentially a single phase and from conventional L ⁇ phases in that it has a wider d-spacing.
  • Structured surfactant systems having dispersed lamellar or spherulitic phases are typically formed by the interaction of surfactants with dissolved electrolyte salts or bases. From the WO 2007/085410 A1 For example, structured hand dishwashing or scouring agents are known.
  • EP 452 106 A2 and US 5,952,285 A refer to flowable, concentrated and aqueous surfactant compositions with anionic surfactant, nonionic surfactant, co-surfactant and inorganic salt. It will be eg in EP 452 106 A2 Surfactant compositions containing alkyl ether sulfate and alkylbenzenesulfonate as anionic surfactant, alkylamine oxide as nonionic surfactant, lauryl ethoxylate with 3 units of ethylene oxide as co-surfactant and potassium carbonate as inorganic salt.
  • an internally structured detergent or cleaning agent with yield point is obtained.
  • This washing or cleaning agent is able to disperse particles stably without the addition of a polymeric thickener.
  • the ability to dispense with polymeric thickeners not only has the advantage that the funds can be made easier and cheaper, but also unwanted side effects of a polymeric thickener, such as graying in the treatment of textiles can be avoided. Accordingly, in a preferred embodiment, the detergent or cleaning agent is free of polymeric thickener.
  • the washing or cleaning agent is stable even without the addition of another polymeric stabilizer or dispersant.
  • the detergents or cleaning agents can be used without problems in machine washing or cleaning agents, since their content of inorganic salt is significantly reduced compared to detergents or cleaners known in the prior art.
  • the anionic surfactant is selected from the group consisting of C 9-13 alkyl benzene sulfonates, olefin sulfonates, C 12-18 alkanesulfonates, ester sulfonates, alk (en) yl sulfates, fatty alcohol ether sulfates, and mixtures thereof.
  • Liquid washing or cleaning compositions which comprise as anionic surfactant C 9-13- alkylbenzenesulfonates and fatty alcohol ether sulfates have particularly good dispersing properties.
  • the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, calcium chloride, magnesium chloride and mixtures thereof, since these salts are very soluble in water.
  • the co-surfactant is an alkoxylation degree ⁇ 3.
  • the washing or cleaning agent additionally contains dispersed particles.
  • the washing or cleaning agent contains at least one enzyme.
  • the use of enzymes in detergents has been known and standard for many years.
  • the protease itself and other enzymes are proteins
  • the protease in liquid detergents tends to self-degrade or degrade other enzymes.
  • stabilization of enzymes is required, especially in liquid systems. In the prior art, this is usually done by the inhibition of the protease, in which the active center is reversibly blocked.
  • Such stabilization is usually achieved by borax, boric acids, boronic acids or their salts or esters and / or by the use of polyols.
  • the liquid structured detergents or cleaners can be used to increase the stability of enzymes. It has been found that the use of conventional enzyme stabilizers can be reduced, and even that the use of conventional enzyme stabilizers can be dispensed with altogether.
  • liquid structured and enzyme-containing washing or cleaning agents are free from borax, boric acids, boronic acids or their salts or esters.
  • borax include, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the abovementioned compounds.
  • 4-FPBA 4-formylphenylboronic acid
  • liquid detergents or cleaning agents stabilizer for enzymes in liquid detergents or cleaning agents are polyols, especially glycerol and 1,2-propylene glycol. Surprisingly, it has been found that such polyols in the liquid structured detergents or cleaners are not required for the stabilization of enzymes. In a further preferred embodiment of the invention, therefore, the liquid washing or cleaning agents according to the invention are free of glycerol and 1,2-propylene glycol.
  • liquid structured and enzyme-containing detergents or cleaners have neither polymeric thickeners nor borax, boric acids, boronic acids or their salts or esters.
  • liquid structured and enzyme-containing detergents or cleaners have neither glycerol and / or 1,2-propylene glycol nor borax, boric acids, boronic acids or their salts or esters.
  • liquid structured and enzyme-containing detergents or cleaners neither glycerol and / or 1,2-propylene glycol nor polymeric thickeners nor borax, boric acids, boronic acids or their salts or esters.
  • the invention relates to the use of the washing or cleaning agent according to the invention for washing and / or cleaning textile fabrics or hard surfaces.
  • the liquid washing or cleaning agent contains an anionic surfactant, a nonionic surfactant, an inorganic salt and a co-surfactant.
  • anionic surfactant sulfonates and / or sulfates are used.
  • the content of anionic surfactant is 5 to 20 wt .-% and preferably 8 to 15 wt .-%, each based on the total washing or cleaning agent.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 16 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -18 fatty alcohols with 1 to 4 EO are suitable.
  • the liquid detergent or cleaning agent contains a mixture of sulfonate and sulfate surfactants.
  • the liquid washing or cleaning agent C contains 9-13- alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant.
  • the ratio of the sulfate surfactants to sulfonate surfactants is preferably in the range of 3: 1 to 1: 3, and more preferably in the range of 3: 1 to 1: 1.
  • the liquid washing or cleaning agent contains fatty alcohol ether sulfates and C 9-13 -alkylbenzenesulfonates in the ratio 2: 1.
  • the liquid washing or cleaning agent may also contain soaps.
  • soaps Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts.
  • the anionic surfactants are in the form of their sodium salts.
  • Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.
  • the amount of soap in the liquid washing or cleaning agent is preferably up to 5% by weight and more preferably up to 2% by weight, based on the total amount of detergent or cleaning agent.
  • the washing or cleaning agent contains not only the anionic surfactant but also nonionic surfactant.
  • the nonionic surfactant includes alkoxylated fatty alcohols having a degree of alkoxylation ⁇ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • the nonionic surfactant used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 5 EO or 7 EO and mixtures of these.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • a mixture of a (more) branched ethoxylated fatty alcohol and a unbranched ethoxylated fatty alcohol such as a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the washing, cleaning, after-treatment or washing assistant contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as nonionic surfactant.
  • the content of nonionic surfactant is 1 to 15 wt .-% and preferably 2 to 10 wt .-%, each based on the total washing or cleaning agent.
  • the total amount of anionic and nonionic surfactant in the liquid washing or cleaning agent is up to 35 wt .-%, preferably up to 15 wt .-%, based on the total liquid detergent or cleaning agent.
  • Another essential constituent of the washing or cleaning agent according to the invention is the inorganic salt. This is, depending on the surfactant system used in an amount of 0.5 to 10 wt .-%, preferably in an amount of 1 to 8 wt .-% and most preferably 2 to 5 wt .-%, each based on the total Detergents or cleaning agents used.
  • Preferred inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride, and mixtures thereof. Particularly stable washing or cleaning agents are obtained when using sodium chloride or mixtures of sodium chloride and potassium sulfate.
  • the inorganic salt promotes the formation of lamellar structures.
  • the inorganic salt has an influence on the viscosity of the washing or cleaning agent and with the aid of the inorganic salt, the viscosity can be adjusted so that the detergent or cleaning agent is easy to dose and a container with the detergent or cleaning a good residual emptying having.
  • the washing or cleaning agent according to the invention necessarily contains a co-surfactant which is selected from the group consisting of alkoxylated C 8 -C 18 fatty alcohols having a degree of alkoxylation ⁇ 3, aliphatic C 6 -C 14 -alcohols, aromatic C 6 -C 14 Alcohols, aliphatic C 6 -C 12 dialcohols, monoglycerides of C 12 -C 18 fatty acids, monoglycerol ethers of C 8 -C 18 fatty alcohols and mixtures thereof.
  • a co-surfactant which is selected from the group consisting of alkoxylated C 8 -C 18 fatty alcohols having a degree of alkoxylation ⁇ 3, aliphatic C 6 -C 14 -alcohols, aromatic C 6 -C 14 Alcohols, aliphatic C 6 -C 12 dialcohols, monoglycerides of C 12 -C 18 fatty acids, monoglycerol ethers of C 8 -C 18
  • This co-surfactant is used in an amount of 0.5 to 5 wt .-%, preferably in an amount of 1 to 4.5 wt .-% and most preferably 2 to 4 wt .-%, each based on the total Detergents or cleaning agents used.
  • Co-surfactants according to this application are amphiphilic molecules with a small, hydrophilic head group. In a binary system with water, these cosurfactants are only weak or even not soluble. Accordingly, they do not form micelles there either. In the presence of the claimed anionic and nonionic surfactants, the co-surfactants are incorporated into their associates and thereby change the morphology of these associates. The spherical micelles become rod-shaped and / or disc-shaped micelles. At a sufficiently high total surfactant content, the desired formation of lamellar phases or structures occurs. Thus, the inorganic salt and the co-surfactant contribute to the formation of the lamellar phases or structures.
  • liquid washing or cleaning agent By adding the inorganic salt and the co-surfactant to the selected surfactant system, an internally structured liquid detergent or cleaning agent with very good dispersing properties.
  • the liquid washing or cleaning agent obtained is extremely stable and shows no phase separation and / or precipitation of the anionic and / or nonionic surfactants.
  • Suitable alkoxylated C 12 -C 18 fatty alcohols having a degree of alkoxylation ⁇ 3 include, for example, iC 13 H 27 O (CH 2 CH 2 O) 2 H, iC 13 H 27 O (CH 2 CH 2 O) 3 H, C 12-14 -Alcohol with 2 EO, C 12-14 -alcohol with 3 EO, C 13-15 -alcohol with 3 EO, C 12-18 -alcohols with 2 EO and C 12-18 -alcohols with 3 EO.
  • Other suitable cosurfactants are 1-hexanol, 1-heptanol, 1-octanol, 1,2-octanediol, stearic monoglycerol and mixtures thereof.
  • Fragrance alcohols such as geraniol are also suitable as co-surfactants.
  • Preferred cosurfactants are C 12 -C 18 fatty alcohols having a degree of alkoxylation ⁇ 3. These cosurfactants are incorporated particularly well into the associates of the anionic and nonionic surfactant.
  • the washing or cleaning agent additionally contains a C 12 -C 18 fatty acid.
  • C 12 -C 18 fatty acids can have a positive influence on the formation of lamellar structures or phases and in particular support their formation. It may be particularly preferred that the washing or cleaning agent contains the neutralized and unneutralized form of a C 12 -C 18 fatty acid.
  • Suitable C 12 -C 18 fatty acids include lauric, myristic, palmitic, stearic, (hydrogenated) erucic acid, behenic coconut fatty acid, palm kernel fatty acid, olive oil fatty acid and / or tallow fatty acid.
  • the determination of the content of the non-neutralized fatty acid content in a liquid detergent or cleaning agent containing fatty acids can be carried out experimentally (for example by means of titration) or with knowledge of the pKa value of the fatty acid used using the Henderson-Hasselbalch equation.
  • the fatty acid soap may be derived from a different fatty acid than the C 12 -C 18 fatty acid used to further aid in the formation of lamellar structures or phases.
  • the washing or cleaning agent may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent.
  • the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, Graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.
  • the washing or cleaning agent is free of polymeric thickener.
  • Suitable builders which may be present in the washing or cleaning agent are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • citric acid adipic acid
  • succinic acid glutaric acid
  • malic acid tartaric acid
  • maleic acid fumaric acid
  • sugar acids aminocarboxylic acids
  • NTA nitrilotriacetic acid
  • MGDA methylglycinediacetic acid
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • soluble builders such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the liquid detergents or cleaners.
  • the liquid washing or cleaning agent contains an enzyme or a mixture of enzymes.
  • the most important detergent enzyme is protease.
  • proteases especially those of the class of the hydrolases such as the (poly) esterases, lipases, amylases, glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, mannanases, perhydrolases, oxireductases and / or laccases are suitable.
  • the amount of enzyme or of the enzymes is from 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%, based on the total detergent or cleaning agent.
  • the enzymes are preferably used as enzyme liquid formulation (s).
  • the repetition length of the lamellar phase is between 10 and 20 nm, preferably 11 to 16 nm and with even greater preference 12 to 14 nm. Such repetition lengths can be calculated, for example, from small-angle X-ray scattering measurements (SAXS).
  • the detergents or cleaners are liquid and contain water as the main solvent. It is preferred that the washing or cleaning agent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent or cleaning agent, water contains.
  • nonaqueous solvents can be added to the washing or cleaning agent.
  • Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol
  • a washing or cleaning agent may contain dispersed particles whose diameter along their greatest spatial extent is preferably 1 to 1000 ⁇ m.
  • particles may be capsules, abrasives as well as powders, granules or compounds of compounds which are insoluble in the washing or cleaning agent, with capsules being preferred.
  • capsule on the one hand understood aggregates with a core-shell structure and on the other hand aggregates with a matrix.
  • Core-shell capsules contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s).
  • the capsules may include, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, detergency boosters, vitamins, proteins , Foam inhibitors and UV absorbers are located.
  • the fillings of the capsules may be solids or liquids in the form of solutions or emulsions or suspensions.
  • the capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent can be between 1 ⁇ m and 1000 ⁇ m, depending on the components contained in their interior and the application.
  • particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles”.
  • the matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials.
  • An exemplary matrix-forming material is alginate.
  • Alginatbasierter speckles is an aqueous alginate solution which also contains the entrapped active ingredient or active ingredients to be entrapped, and then dripped 2+ or Al 3+ ions cured precipitation bath containing Ca in a.
  • matrix-forming materials can be used instead of alginate.
  • the particles can be stably dispersed in the liquid detergents or cleaners.
  • Stable means that the detergents or cleaning agents are stable at room temperature for a period of at least 4 weeks, and preferably for at least 6 weeks, without the particles in the medium creaming or sedimenting.
  • the release of the active ingredients from the capsules is usually carried out by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.
  • liquid detergents or cleaners contain capsules in which one or more fragrances are contained.
  • the particles may comprise abrasives such as plastic or calcium carbonate beads as well as powders, granules or compounds of compounds insoluble in the detergent or cleaning agent.
  • abrasives such as plastic or calcium carbonate beads as well as powders, granules or compounds of compounds insoluble in the detergent or cleaning agent.
  • the liquid washing or cleaning agent contains identical or different particles in amounts of 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-% and most preferably 0.2 to 5 wt. -%.
  • the washing or cleaning agent can be used for washing and / or cleaning fabrics or hard surfaces.
  • the constituents of the washing or cleaning agents can be mixed in stirred tanks, initially water is introduced. Then the nonaqueous solvents and surfactants, including the cosurfactant, are added. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid moiety and the neutralization of the anionic surfactants are used, which are used in the acid form. Then the other ingredients, preferably in portions, are added.
  • the inorganic salt may be added as a solid or in the form of a concentrated solution at various times in the manufacturing process.
  • the flow limits of the detergents or cleaning agents were measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called shear stress controlled rheometer.
  • the flow limits in the context of the present invention were determined as follows at 23 ° C.
  • the samples were loaded in the rheometer with a time-increasing shear stress s (t).
  • t time-increasing shear stress
  • the shear stress can be increased in the course of 10 minutes from the smallest possible value (eg 2 mPa) to eg 10 Pa.
  • the deformation y of the sample is measured.
  • the deformation is plotted against the shear stress in a log-log plot. If the examined sample has a yield point, clearly two areas can be distinguished in this plot. Below a certain shear stress, one finds a purely elastic deformation.
  • the slope of the curve ⁇ ( ⁇ ) (log-log plot) in this area is one.
  • Table 1 below shows the compositions of three inventive detergents or cleaners E1 to E3 and the composition of a comparative example V1 (All amounts are in wt .-% active, based on the total washing or cleaning agent, indicated).
  • Table 1 Wt .-% ingredients V1 E1 E2 E3 C 12 -C 18 ROH with 7 EO 2 2 2 4 Na lauryl ether sulfate (2 EO) 8th 8th 8th 8th C 12 -C 18 fatty acid 1 1 1 1 1 linear C 9-13 -alkylbenzenesulfonic acid, sodium salt 4 4 4 4 4 Phosphonic acid, Na salt 0.8 0.8 0.8 0.8 Optical brightener 0.1 0.1 0.1 0.1 0.1 0.1 Silicone antifoam 0.02 0.02 0.02 citric acid 2.5 2.5 2.5 2.5 2.5 boric acid 1.1 1.1 1.0 ethanol 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
  • the three detergents E1 to E3 were stable at room temperature for 6 weeks.
  • washing or cleaning agent E2 showed no significant creaming and / or sedimentation of the dispersed capsules.
  • Comparative Example C1 clearly shows that the use of inorganic salt alone does not lead to a liquid washing or cleaning agent having a yield point.
  • the inorganic salt is present in the claimed amount range, but since the co-surfactant is missing, the resulting detergent or cleaning agent has no yield point.
  • the washing or cleaning agent V1 separates into two phases.

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (15)

  1. Produit de lavage ou de nettoyage liquide à limite d'écoulement, contenant :
    - 5 à 20 % en poids de tensioactif anionique choisi dans le groupe comportant des tensioactifs sulfonates, des tensioactifs sulfates et leurs mélanges,
    - 1 à 15 % en poids de tensioactif non-ionique choisi dans le groupe comportant des alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, des esters alkylique d'acides gras alcoxylés, des amides d'acides gras, des amides d'acides gras alcoxylés, des amides de polyhydroxyacides gras, des éthers alkylphénol polyglycoliques, des oxydes d'amine, des alkylpolyglucosides et des mélanges de ceux-ci,
    - 0,5 à 10 % en poids d'un sel minéral, et
    - 0,5 à 5 % en poids d'un co-tensioactif choisi dans le groupe comportant des alcools gras en C8-18 alcoxylés ayant un degré d'alcoxylation ≤ 3, des alcools en C6-14 aliphatiques, des alcools en C6-14 aromatiques, des diols en C6-12 aliphatiques, des monoglycérides d'acides gras en C12-18, des monoéthers de glycérol d'alcools gras en C8-18 et de leurs mélanges,
    le tensioactif non-ionique contenu étant au moins un composé choisi parmi des alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, et
    ledit co-tensioactif contenu étant au moins un composé choisi dans le groupe comportant des'alcools gras en C12-18 alcoxylés ayant un degré d'alcoxylation ≤ 3, des alcools en C6-14 aliphatiques et de leurs mélanges.
  2. Produit de lavage ou de nettoyage liquide selon la revendication 1, caractérisé en ce que le tensioactif anionique est choisi dans le groupe comportant des benzène-sulfonates d'alkyle en C9-13, des oléfine-sulfonates, C12-18-alcane sulfonates, estersulfonates, des sulfates de l'alkyl(èn)e, des éthersulfates d'alcools gras et de leurs mélanges.
  3. Produit de lavage ou de nettoyage liquide selon la revendication 2, caractérisé en ce que le tensioactif anionique comprend des benzène sulfonates de alkyle en C9-13-et des éthersulfates d'alcools gras.
  4. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 3, caractérisé en ce que le sel minéral est choisi dans le groupe comportant le chlorure de sodium, le chlorure de potassium, le sulfate de sodium, le carbonate de sodium, le sulfate de potassium, le carbonate de potassium, l'hydrogénocarbonate de sodium, l'hydrogénocarbonate de potassium, le chlorure de calcium, le chlorure de magnésium et leurs mélanges.
  5. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 4, caractérisé en ce que le co-tensioactif est un alcool gras en C12-18 ayant un degré d'alcoxylation ≤ 3.
  6. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 5, caractérisé en ce que le produit de lavage ou de nettoyage contient des particules dispersées.
  7. Produit de lavage ou de nettoyage liquide selon la revendication 6, caractérisé en ce que les particules dispersées sont des capsules, des substances abrasives et/ou des constituants insolubles du produit de lavage ou de nettoyage.
  8. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 7, caractérisé en ce que le produit de lavage ou de nettoyage ne contient pas d'épaississant.
  9. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 8, caractérisé en ce que le produit de lavage ou de nettoyage contient en plus un acide gras en C12-18.
  10. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 9, caractérisé en ce qu'il contient au moins une enzyme.
  11. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 10, caractérisé en ce qu'il ne contient pas de borax, d'acides boriques, d'acides boroniques ou de sels ou d'esters de ceux-ci.
  12. Produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 11, caractérisé en ce qu'il ne contient pas de glycérol et/ou de 1,2-propylèneglycol.
  13. Utilisation du produit de lavage ou de nettoyage liquide selon l'une des revendications 1 à 12 pour laver et/ou nettoyer des structures textiles planes ou des surfaces dures.
  14. Utilisation d'une combinaison de 0,5 à 10 % en poids d'un sel minéral et de 0,5 à 5 % en poids d'un co-tensioactif pour produire une limite d'écoulement dans un produit de lavage ou de nettoyage liquide contenant :
    - 5 à 20 % en poids d'un tensioactif anionique choisi dans le groupe comprenant des tensioactifs sulfonates, des tensioactifs sulfates et leurs mélanges,
    - 1 à 15 % en poids d'un tensioactif non-ionique choisi dans le groupe comportant des alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, d'esters alkyliques d'acides gras alcoxylés, des amides d'acides gras, des amides d'acides gras alcoxylés, des amides de polyhydroxyacides gras, des éthers alkylphénol polyglycoliques, des oxydes d'amine, des alkylpolyglucosides et de leurs mélanges,
    le tensioactif non-ionique contenu étant au moins un composé choisi parmi des alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, et
    le co-tensioactif étant choisi dans le groupe comportant des alcools gras en C12-18alcoxylés ayant un degré d'alcoxylation ≤ 3, des alcools en C6-14 aliphatiques et des mélanges de ceux-ci.
  15. Procédé de fabrication d'un produit de lavage ou de nettoyage liquide à limite d'écoulement, contenant :
    - 5 à 20 % en poids d'un tensioactif anionique choisi dans le groupe comportant des tensioactifs sulfonates, des tensioactifs sulfates et des mélanges de ceux-ci, et
    - 1 à 15 % en poids de tensioactif non-ionique choisi dans le groupe comportant des alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, des esters alkylique d'acides gras alcoxylés, des amides d'acides gras, des amides d'acides gras alcoxylés, des amides de polyhydroxyacides gras, des éthers alkylphénol polyglycoliques, desoxydes d'amine, des alkylpolyglucosides et des mélanges de ceux-ci, le tensioactif non-ionique contenu étant au moins un composé choisi parmi les alcools gras alcoxylés ayant un degré d'alcoxylation ≥ 4, et
    dans lequel on ajoute au produit de lavage ou de nettoyage liquide 0,5 à 10 % en poids d'un sel minéral et 0,5 à 5 % en poids d'un co-tensioactif choisi dans le groupe comportant des alcools gras en C8-18 alcoxylés ayant un degré d'alcoxylation ≤ 3, des alcools en C6-14 aliphatiques, des alcools en C6-14 aromatiques, de diols en C6-12 aliphatiques, des monoglycérides d'acides gras en C12-18, des monoéthers de glycérol d'alcools gras en C8-18 et des mélanges de ceux-ci, ledit co-tensioactif ajouté étant au moins un composé choisi dans le groupe comportant des alcools gras en C12-18alcoxylés ayant un degré d'alcoxylation ≤ 3, des alcools en C6-14aliphatiques et de des mélanges de ceux-ci.
EP12773309.5A 2011-11-02 2012-10-12 Produit de lavage ou de nettoyage structuré à limite d'écoulement Revoked EP2773736B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201110085638 DE102011085638A1 (de) 2011-11-02 2011-11-02 Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze II
DE201210201980 DE102012201980A1 (de) 2012-02-10 2012-02-10 Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze
PCT/EP2012/070329 WO2013064357A1 (fr) 2011-11-02 2012-10-12 Produit de lavage ou de nettoyage structuré à limite d'écoulement

Publications (2)

Publication Number Publication Date
EP2773736A1 EP2773736A1 (fr) 2014-09-10
EP2773736B1 true EP2773736B1 (fr) 2018-10-10

Family

ID=47040718

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12773309.5A Revoked EP2773736B1 (fr) 2011-11-02 2012-10-12 Produit de lavage ou de nettoyage structuré à limite d'écoulement

Country Status (4)

Country Link
US (1) US9023786B2 (fr)
EP (1) EP2773736B1 (fr)
KR (1) KR102017917B1 (fr)
WO (1) WO2013064357A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2773736B1 (fr) 2011-11-02 2018-10-10 Henkel AG & Co. KGaA Produit de lavage ou de nettoyage structuré à limite d'écoulement
CN103820247A (zh) * 2014-03-17 2014-05-28 苏州龙腾万里化工科技有限公司 一种新型中性清洗剂
BR112017003309B1 (pt) * 2014-08-29 2022-02-08 Unilever Ip Holdings B.V. Composição de detergente líquido, processo de redução de espuma durante o enxágue na lavagem de louça e uso de uma composição
DE102014225145A1 (de) 2014-12-08 2016-06-09 Henkel Ag & Co. Kgaa Verfahren zur Herstellung flüssiger, Tensid-enthaltender Zusammensetzungen mit Fließgrenze
DE102015207534A1 (de) 2015-04-24 2016-10-27 Henkel Ag & Co. Kgaa Verfahren zur Herstellung von Kapseln mit einer polymeren Matrix
DE102015212131A1 (de) * 2015-06-30 2017-01-05 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer flüssigen, Tensid enthaltenden Zusammensetzung
DE102016202804A1 (de) * 2016-02-24 2017-08-24 Henkel Ag & Co. Kgaa Optimierte Tensid-Enzym Mischungen
DE102017215016A1 (de) 2017-08-28 2019-02-28 Henkel Ag & Co. Kgaa Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze
CN109354368A (zh) * 2018-11-22 2019-02-19 国网天津市电力公司电力科学研究院 一种变电站事故油池含油污泥处理方法
EP3670639A1 (fr) * 2018-12-17 2020-06-24 Unilever N.V. Formulation liquide pour lave-vaisselle à main contenant un acide gras hydroxy et un polymère
EP3898914B1 (fr) * 2018-12-17 2022-03-23 Unilever IP Holdings B.V. Formulation liquide de lavage de la vaisselle à la main comprenant des acides gras et polymère
WO2020126601A1 (fr) * 2018-12-17 2020-06-25 Unilever N.V. Formulation liquide de lavage de vaisselle à la main comprenant des acides gras et un polymère
DE102019126124A1 (de) 2019-09-27 2021-04-01 Henkel Ag & Co. Kgaa Verfahren zur Herstellung Tensid enthaltender Zusammensetzungen in einem sequenziellen Verfahren
US11608479B2 (en) 2020-07-23 2023-03-21 Henkel Ag & Co. Kgaa Washing agent preparation with improved optical and rheological properties
US11441100B2 (en) * 2020-07-23 2022-09-13 Henkel Ag & Co. Kgaa Opacified and structured liquid laundry detergents containing colloidal particles
US11591553B2 (en) 2020-07-23 2023-02-28 Henkel Ag & Co. Kgaa Method for producing a washing agent portion unit with improved optical and rheological properties
US11873467B2 (en) 2020-07-23 2024-01-16 Henkel Ag & Co. Kgaa Washing agent with improved optical and rheological properties
US11692158B2 (en) * 2020-07-23 2023-07-04 Henkel Ag & Co. Kgaa Washing agent with improved optical and rheological properties
US11680225B2 (en) 2020-07-23 2023-06-20 Henkel Ag & Co. Kgaa Method for producing a washing agent with improved optical and rheological properties
US11566209B2 (en) 2020-07-23 2023-01-31 Henkel Ag & Co. Kgaa Delayed onset fluid gels for use in unit dose laundry detergents containing colloidal particles
US11674114B2 (en) 2020-10-29 2023-06-13 Henkel Ag & Co. Kgaa Method of making an opacified liquid detergent composition using a divalent cation solution
US11873466B2 (en) * 2020-10-29 2024-01-16 Henkel Ag & Co. Kgaa Opacified liquid detergent composition comprising a fatty acid/calcium salt mixture
WO2023237299A1 (fr) * 2022-06-09 2023-12-14 Unilever Ip Holdings B.V. Compositions détergentes liquides aqueuses pour le lavage de la vaisselle

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301883A1 (fr) 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides
WO1991003541A1 (fr) 1989-09-06 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Detergents liquides a teneur en zeolite
EP0452106A2 (fr) * 1990-04-10 1991-10-16 ALBRIGHT & WILSON UK LIMITED Composition aqueuse d'un tensio-actif
EP0623670A2 (fr) 1993-05-07 1994-11-09 ALBRIGHT & WILSON UK LIMITED Compositions tensioactives à base aqueuse
WO2005049775A1 (fr) * 2003-11-14 2005-06-02 The Procter & Gamble Company Composition detergente liquide comportant un tensioactif non ionique de solubilisation
WO2006021255A1 (fr) 2004-08-23 2006-03-02 Henkel Kommanditgesellschaft Auf Aktien Detergent ou nettoyant clair, a limite d'ecoulement
WO2013064357A1 (fr) 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa Produit de lavage ou de nettoyage structuré à limite d'écoulement

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723431A (en) * 1989-09-22 1998-03-03 Colgate-Palmolive Co. Liquid crystal compositions
US5952285A (en) * 1990-04-10 1999-09-14 Albright & Wilson Limited Concentrated aqueous surfactant compositions
US6399563B1 (en) * 1999-03-24 2002-06-04 Colgate-Palmolive Co. All purpose liquid cleaning compositions
US7273570B2 (en) 2005-07-08 2007-09-25 Eastman Kodak Company Method of forming polymer particles
ES2558227T3 (es) * 2008-06-19 2016-02-02 Dsm Ip Assets B.V. Preparaciones de champús

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301883A1 (fr) 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides
WO1991003541A1 (fr) 1989-09-06 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Detergents liquides a teneur en zeolite
EP0452106A2 (fr) * 1990-04-10 1991-10-16 ALBRIGHT & WILSON UK LIMITED Composition aqueuse d'un tensio-actif
EP0623670A2 (fr) 1993-05-07 1994-11-09 ALBRIGHT & WILSON UK LIMITED Compositions tensioactives à base aqueuse
WO2005049775A1 (fr) * 2003-11-14 2005-06-02 The Procter & Gamble Company Composition detergente liquide comportant un tensioactif non ionique de solubilisation
WO2006021255A1 (fr) 2004-08-23 2006-03-02 Henkel Kommanditgesellschaft Auf Aktien Detergent ou nettoyant clair, a limite d'ecoulement
WO2013064357A1 (fr) 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa Produit de lavage ou de nettoyage structuré à limite d'écoulement

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Rheological Techniques for Yield Stress Analysis", TA INSTRUMENTS MANUAL RH025, pages 1 - 5
TONY HARGREAVES: "Chemical Formulations", 2003, THE ROYAL SOCIETY OF CHEMISTRY, Cambridge, pages: 75 - 76 *

Also Published As

Publication number Publication date
US20140235524A1 (en) 2014-08-21
WO2013064357A1 (fr) 2013-05-10
US9023786B2 (en) 2015-05-05
KR20140091534A (ko) 2014-07-21
KR102017917B1 (ko) 2019-09-03
EP2773736A1 (fr) 2014-09-10

Similar Documents

Publication Publication Date Title
EP2773736B1 (fr) Produit de lavage ou de nettoyage structuré à limite d'écoulement
EP2773735B1 (fr) Composition detergente structurée à limite d'écoulement
DE19752163A1 (de) Niedrigkonzentrierte höherviskose Flüssigwaschmittel
EP3317391B1 (fr) Procédé de préparation d'une composition liquide contenant un tensioactif
EP3167040B1 (fr) Procédé de lavage
DE102011085638A1 (de) Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze II
DE68922263T2 (de) Flüssige Waschmittelzusammensetzungen.
EP3116984B1 (fr) Mélange de tensioactifs amélioré ayant un degré d'éthoxylation optimisé
EP3230430B1 (fr) Procédé de production de compositions liquides à limite d'écoulement contenant des agents tensioactifs
WO2014086634A1 (fr) Détergent structuré à limite d'écoulement
DE102011085639A1 (de) Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze
DE102016204390A1 (de) Verfahren zum Reinigen von Wäsche in einer Waschmaschine sowie eine Waschmaschine
DE102006034902A1 (de) Wasch- oder Reinigungsmittel mit verbessertem Dispergievermögen
WO2017050821A1 (fr) Composition contenant des tensioactifs pour le traitement de textiles avec un colorant
EP3525924B1 (fr) Composition de détergents à limite d'écoulement
CH635614A5 (en) Liquid detergent and process for its preparation
EP2716747A1 (fr) Mélange des agents tensioactifs tres performant et composition detergente le contenant
DE102012201980A1 (de) Strukturiertes Wasch- oder Reinigungsmittel mit Fließgrenze
WO2014053365A1 (fr) Détergents plus puissants dotés d'agents complexants i
EP2706109B1 (fr) Mélange tensioactif stabilisant les enzymes et produit de lavage ou de nettoyage liquide les contenant
WO2014053367A1 (fr) Détergents dotés d'agents complexants ii, de performance améliorée
DE102016204268A1 (de) Waschmittelzusammensetzung
DE19752454A1 (de) Geschirrspülmittel mit spezifischem Viskositätsprofil

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: 20140225

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170120

TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180608

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1051238

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502012013600

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181010

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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: 20181010

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

Ref country code: PL

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: 20181010

Ref country code: NO

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: 20190110

Ref country code: LT

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: 20181010

Ref country code: IS

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: 20190210

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: 20181010

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: 20181010

Ref country code: BG

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: 20190110

Ref country code: LV

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: 20181010

Ref country code: HR

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: 20181010

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: 20181010

Ref country code: AL

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: 20181010

Ref country code: PT

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: 20190210

Ref country code: RS

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: 20181010

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: 20190111

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181031

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: 20181012

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502012013600

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

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: 20181010

Ref country code: CZ

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: 20181010

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 PRESCRIBED TIME-LIMIT

Effective date: 20181010

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

Free format text: ORIGINAL CODE: 0009299OPPO

26 Opposition filed

Opponent name: DALLI-WERKE GMBH & CO. KG

Effective date: 20190709

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20190709

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

Ref country code: CH

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

Effective date: 20181031

Ref country code: LI

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

Effective date: 20181031

Ref country code: RO

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: 20181010

Ref country code: SM

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: 20181010

Ref country code: EE

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: 20181010

Ref country code: SK

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: 20181010

Ref country code: MC

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: 20181010

Ref country code: BE

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

Effective date: 20181031

R26 Opposition filed (corrected)

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20190709

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: 20181012

Ref country code: SI

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: 20181010

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1051238

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181012

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: 20181012

Ref country code: MT

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: 20181010

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

Ref country code: TR

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: 20181010

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

Ref country code: HU

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

Effective date: 20121012

Ref country code: MK

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

Effective date: 20181010

Ref country code: CY

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: 20181010

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

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

Ref country code: GB

Payment date: 20201022

Year of fee payment: 9

Ref country code: DE

Payment date: 20201022

Year of fee payment: 9

Ref country code: FR

Payment date: 20201022

Year of fee payment: 9

APBG Information on invitation to file observation in appeal deleted

Free format text: ORIGINAL CODE: EPIDOSDOBA2O

APBY Invitation to file observations in appeal sent

Free format text: ORIGINAL CODE: EPIDOSNOBA2O

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502012013600

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502012013600

Country of ref document: DE

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

REG Reference to a national code

Ref country code: FI

Ref legal event code: MGE

27W Patent revoked

Effective date: 20210615

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20210615

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 1051238

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210615