EP2812421B1 - Washing or cleaning agent with cellulose or a cellulose derivative - Google Patents

Washing or cleaning agent with cellulose or a cellulose derivative Download PDF

Info

Publication number
EP2812421B1
EP2812421B1 EP13700094.9A EP13700094A EP2812421B1 EP 2812421 B1 EP2812421 B1 EP 2812421B1 EP 13700094 A EP13700094 A EP 13700094A EP 2812421 B1 EP2812421 B1 EP 2812421B1
Authority
EP
European Patent Office
Prior art keywords
acid
treated
cellulose
cleaning agent
washing
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.)
Not-in-force
Application number
EP13700094.9A
Other languages
German (de)
French (fr)
Other versions
EP2812421A1 (en
Inventor
Georg Meine
Cornelius Bessler
Andrea Eutebach
Frank Sonnenschein
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2812421A1 publication Critical patent/EP2812421A1/en
Application granted granted Critical
Publication of EP2812421B1 publication Critical patent/EP2812421B1/en
Not-in-force 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the invention relates to a liquid washing or cleaning agent containing surfactant (s) and a cellulose or a cellulose derivative.
  • the invention also relates to processes for the preparation of the washing or cleaning agent.
  • detergents or cleaners To increase the washing or cleaning performance of detergents or cleaners they often contain one or more additives.
  • detergents in order to prevent re-release of previously released soil in finer distribution (redeposition), detergents contain so-called graying inhibitors, such as carboxymethylcellulose.
  • EP 054325 A1 a detergent with carboxymethylcellulose as a grayness inhibitor.
  • GB 729531 A Liquid detergents with acidic cellulose sulfates are proposed.
  • DE 10 2007 021 793 A1 relates to detergents comprising surfactant, graying-inhibiting polysaccharide having a particle size of less than 100 nm and other conventional ingredients.
  • liquid detergents or cleaners have increasingly been offered in transparent bottles. Due to the low solubility of carboxymethylcellulose in liquid detergents or cleaners, incorporation of carboxymethylcellulose into liquid detergents or cleaners results in turbidity: this leads to an aesthetically less appealing product, especially if it is offered in a transparent bottle.
  • Another problem is that stable dispersions of cellulose or cellulose derivatives in the matrix of a detergent or cleaning agent are very difficult to obtain.
  • the incorporability into a liquid matrix of a washing or cleaning agent can be improved by an acid treatment of cellulose or a cellulose derivative without losing the graying-inhibiting property of the cellulose or of the cellulose derivative.
  • the improved incorporability of aesthetically pleasing liquid detergents or cleaners are obtained with graying-inhibiting property.
  • the agent is an acid-treated cellulose derivative selected from the group consisting of acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid ester salt, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose and a mixture of these acid-treated cellulose derivatives.
  • CMC carboxymethylcellulose
  • an acid-treated cellulose acid sulfonic acid ester salt acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyeth
  • These acid-treated cellulose derivatives can be incorporated in a particularly stable and uniform manner in the liquid matrix of a washing or cleaning agent.
  • the acid-treated cellulose derivative is acid-treated carboxymethylcellulose (CMC) and / or acid-treated hydroxypropylmethylcellulose. Particularly preferred is the acid-treated carboxymethyl cellulose acid-treated sodium carboxymethyl cellulose.
  • the amount of acid-treated cellulose or acid-treated cellulose derivative is from 0.01% to 10% by weight, and more preferably from 0.1% to 8% by weight, based on the total liquid detergent or cleaning agent.
  • cellulose or cellulose derivative have proven to be particularly advantageous. At a level of 0.01% by weight, no graying-inhibiting effect can be observed, and at amounts greater than 8% by weight, no further increase in the graying-inhibiting effect of the liquid detergent or cleaning agent can be observed.
  • the acid-treated cellulose or the acid-treated cellulose derivative has been treated with an alkylbenzene sulfonic acid.
  • the salts of alkylbenzenesulfonic acid are commonly used anionic surfactants in liquid detergents or cleaners.
  • alkylbenzenesulfonic acid as the acid in the acid treatment, on the one hand, no additional chemical must be used and the acid-treated cellulose or the acid-treated cellulose derivative can be used directly, ie without further workup, in the preparation of the liquid detergent or cleaning agent be used. This makes the preparation of the liquid detergent or cleaning agent particularly effective.
  • the invention relates to the use of a correspondingly acid-treated cellulose or a corresponding acid-treated cellulose derivative in a liquid washing or cleaning agent to increase the anti-graying performance of the washing or cleaning agent.
  • the liquid washing or cleaning agent contains an acid-treated cellulose or an acid-treated cellulose derivative, each of which has been treated with an alkylbenzenesulfonic acid.
  • the corresponding acid-treated cellulose derivative is preferably acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid salt, acid-treated cellulose acid acid sulfate, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose or the like Mixture of these acid-treated cellulose derivatives. Very particular preference is given to the cellulose derivative acid-treated carboxymethylcellulose, in particular acid-treated sodium carboxymethylcellulose, and / or acid-treated hydroxypropylmethylcellulose.
  • the acid-treated cellulose or the acid-treated cellulose derivative is treated with an alkylbenzene sulfonic acid. Particular preference is given to using dodecylbenzenesulfonic acid and / or C 10 -C 13 -alkylbenzenesulfonic acid for the acid treatment of the cellulose or of the cellulose derivative.
  • the amount of acid-treated cellulose or acid-treated cellulose derivative is preferably 0.01 to 10 wt .-%, and more preferably 0.1 to 8 wt .-%, each based on the total liquid detergent or cleaning agent.
  • the acid treatment of the cellulose or the cellulose derivative is carried out by grinding with an alkylbenzenesulfonic acid. It is preferred that the grinding process takes place in a ball mill. In this embodiment, it is advantageous if the amount of alkylbenzenesulfonic acid is from 0.01 to 50% by weight, and more preferably from 0.1 to 5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture.
  • the amount of cellulose (derivative) is 50 to 99.99% by weight and more preferably 95 to 99.9% by weight, in each case based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture, is.
  • a solvent is present in addition to the cellulose or the cellulose derivative and the alkylbenzenesulfonic acid.
  • ethanol is used as the solvent.
  • carboxymethylcellulose especially sodium carboxymethylcellulose, with a C 10 -C 13 -alkylbenzenesulfonic acid by ball milling.
  • Sodium carboxymethylcellulose ground with C 10 -C 13 -alkylbenzenesulfonic acid can be stably incorporated into the matrix of a liquid detergent or cleaning agent without precipitation, creaming, deposits and / or lumps.
  • Liquid detergent or cleaning agent having a C 10 -C 13 alkyl benzene milled sodium carboxymethylcellulose have a high transparency and good graying-inhibiting properties.
  • the acid treatment of a cellulose or a cellulose derivative is carried out by contacting the cellulose or the cellulose derivative with an aqueous solution of an alkylbenzenesulfonic acid with stirring.
  • an alkylbenzenesulfonic acid it is advantageous if, when using an alkylbenzenesulfonic acid, the amount of alkylbenzenesulfonic acid is from 0.1 to 20% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture.
  • the amount of cellulose (derivative) is from 0.01 to 2.5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture. It is preferred to subject hydroxypropylmethylcellulose to such acid treatment with a C 10 -C 13 -alkylbenzenesulfonic acid. Liquid detergents or cleaners with a C 10 -C 13 -alkylbenzenesulfonic acid treated hydroxypropylmethylcellulose are clear and have good graying-inhibiting properties.
  • the liquid detergent or cleaning agent further contains a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof.
  • a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof.
  • the liquid washing or cleaning agent preferably comprises anionic and nonionic surfactant.
  • the anionic surfactant used may preferably be sulfonates and / or sulfates.
  • 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 15 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.
  • Suitable anionic surfactants are 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 including the soaps may be in the form of their sodium, potassium, magnesium or ammonium salts.
  • Suitable ammonium salts as counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or methylethylamine.
  • the content of anionic surfactant including soaps is preferably from 2 to 40% by weight and more preferably from 5 to 30% by weight, based in each case on the total liquid detergent or cleaning agent.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, 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 is 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 can 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 an 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 particularly preferably contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO or 8 EO as nonionic surfactant.
  • the content of nonionic surfactant is preferably 1 to 40 wt .-% and more preferably 2 to 30 wt .-%, each based on the total liquid detergent or cleaning agent.
  • the total amount of anionic and nonionic surfactant in the liquid washing or cleaning agent is up to 70 wt .-%, preferably up to 50 wt .-%, based on the total liquid detergent or cleaning agent.
  • the liquid detergent or cleaning agent may contain other ingredients that the performance and / or aesthetic properties of the washing or cleaning Cleaner further improve.
  • the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, enzyme stabilizers, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , 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, skincare active ingredients, swelling and anti-slip agents, softening components and UV absorbers.
  • Particularly preferred substances which may be included in the washing or cleaning agent are builders, foam inhibitors, enzymes, perfumes, fluorescers, dyes, enzyme stabilizers and mixtures thereof.
  • Suitable enzymes which may be present in the washing or cleaning agent are, for example, cellulases, amylases, proteases, lipases, mannanases, pectate lyases or xyloglucanases. A particularly good anti-graying performance of the washing or cleaning agent is achieved if the washing or cleaning agent contains a cellulase.
  • the detergents or cleaners are liquid and may contain water as the main solvent. Alternatively, or in addition to the water, the detergents or cleaners may contain non-aqueous solvents.
  • the washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics.
  • liquid washing or cleaning agents with an acid-treated cellulose or an acid-treated cellulose derivative can be used in particular for increasing the anti-graying performance of the washing or cleaning agent during the washing and / or cleaning of textile fabrics.
  • washing or cleaning agent involves first grinding the cellulose or the cellulose derivative with the alkylbenzenesulfonic acid. Subsequently, the resulting mixture is transferred to a stirred tank and water, non-aqueous solvents and the other surfactants, if present, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.
  • Another possibility for the preparation of the washing or cleaning agent provides that first the cellulose or the cellulose derivative is brought into contact with an aqueous solution of the alkylbenzenesulfonic acid with vigorous stirring in a stirred tank. Subsequently, the non-aqueous solvents and the other surfactants, if any, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.
  • Table 1 below shows the compositions of a washing or cleaning agent E1 according to the invention and the compositions of two washing or cleaning compositions V1 and V2 which are not according to the invention.
  • Table 1 Liquid washing or cleaning agents E1 and V1 to V2 [all amounts are given in% by weight of active ingredient, based on the total composition] Wt .-% ingredients E1 V1 V2 C 12 -C 18 ROH (7 EO) 8.4 8.4 8.4 Na lauryl ether sulfate (2 EO) 10.8 10.8 10.8 C 12 -C 18 fatty acid 4.8 4.8 4.8 lin.
  • the hydroxypropyl methylcellulose used was Methocel® K 15 M from The Dow Chemical Company.
  • the acid-treated cellulose derivatives could be incorporated stably and uniformly into the liquid matrix of detergents or cleaners.
  • the resulting liquid washing or cleaning agent E1 was aesthetically much more appealing than the comparison washing or cleaning agent V3.
  • the washing or cleaning agent E1 had a high transparency and the liquid washing or cleaning agent E1 was even clear.
  • the washing and cleaning agent V3 showed no uniform distribution of cellulose derivatives in the liquid matrix, but clearly visible agglomerates of cellulose derivatives.
  • the resulting liquid washing or cleaning agent E1 was stable even after 8 weeks storage under various climatic conditions and showed optical homogeneity, the formulation E1 was even clear.

Landscapes

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

Description

Die Erfindung betrifft ein flüssiges Wasch- oder Reinigungsmittel, enthaltend Tensid(e) und eine Cellulose oder ein Cellulosederivat. Die Erfindung betrifft auch Verfahren zur Herstellung des Wasch- oder Reinigungsmittels.The invention relates to a liquid washing or cleaning agent containing surfactant (s) and a cellulose or a cellulose derivative. The invention also relates to processes for the preparation of the washing or cleaning agent.

Zur Erhöhung der Wasch- oder Reinigungsleistung von Wasch- oder Reinigungsmitteln enthalten diese häufig ein oder mehrere Zusatzstoffe. Um beispielsweise ein Wiederaufziehen von vorher losgelöstem Schmutz in feinerer Verteilung (Redeposition) zu verhindern, enthalten Waschmittel so genannte Vergrauungsinhibitoren, wie zum Beispiel Carboxymethylcellulose.To increase the washing or cleaning performance of detergents or cleaners they often contain one or more additives. For example, in order to prevent re-release of previously released soil in finer distribution (redeposition), detergents contain so-called graying inhibitors, such as carboxymethylcellulose.

So beschreibt die EP 054325 A1 ein Waschmittel mit Carboxymethylcellulose als Vergrauungsinhibitor. In GB 729531 A werden Flüssigwaschmittel mit sauren Cellulosesulfaten vorgeschlagen. DE 10 2007 021 793 A1 betrifft Waschmittel, die Tensid, vergrauungsinhibierendes Polysaccharid mit einer Partikelgröße kleiner 100 nm und weitere übliche Inhaltsstoffe umfassen.That's how it describes EP 054325 A1 a detergent with carboxymethylcellulose as a grayness inhibitor. In GB 729531 A Liquid detergents with acidic cellulose sulfates are proposed. DE 10 2007 021 793 A1 relates to detergents comprising surfactant, graying-inhibiting polysaccharide having a particle size of less than 100 nm and other conventional ingredients.

Seit einigen Jahren werden flüssige Wasch- oder Reinigungsmittel vermehrt in transparenten Flaschen angeboten. Aufgrund der geringen Löslichkeit von Carboxymethylcellulose in flüssigen Wasch- oder Reinigungsmittel kommt es bei Einarbeitung von Carboxymethylcellulose in flüssige Wasch- oder Reinigungsmittel zu Trübungen: Dies führt zu einem ästhetisch wenig ansprechenden Produkt, insbesondere wenn es in einer transparenten Flasche angeboten wird.For some years, liquid detergents or cleaners have increasingly been offered in transparent bottles. Due to the low solubility of carboxymethylcellulose in liquid detergents or cleaners, incorporation of carboxymethylcellulose into liquid detergents or cleaners results in turbidity: this leads to an aesthetically less appealing product, especially if it is offered in a transparent bottle.

Ein weiteres Problem ist, dass stabile Dispersionen von Cellulose oder Cellulosederivaten in der Matrix eines Wasch- oder Reinigungsmittels sehr schwer zu erhalten sind.Another problem is that stable dispersions of cellulose or cellulose derivatives in the matrix of a detergent or cleaning agent are very difficult to obtain.

Es ist deshalb eine Aufgabe der Erfindung, ein flüssiges Wasch-oder Reinigungsmittel mit einer Cellulose oder einem Cellulosederivat bereitzustellen, welches stabil und ästhetisch ansprechend ist.It is therefore an object of the invention to provide a liquid washing or cleaning agent with a cellulose or a cellulose derivative which is stable and aesthetically pleasing.

Diese Aufgabe wird gelöst durch ein flüssiges Wasch- oder Reinigungsmittel, enthaltend

  1. (a) 1 bis 70 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, Tensid(e) und
  2. (b) eine säurebehandelte Cellulose oder ein säurebehandeltes Cellulosederivat, wobei die säurebehandelte Cellulose oder das säurebehandelte Cellulosederivat mit einer Alkylbenzolsulfonsäure behandelt worden sind.
This object is achieved by a liquid washing or cleaning agent containing
  1. (A) 1 to 70 wt .-%, based on the total liquid detergent or cleaning agent, surfactant (s) and
  2. (b) an acid-treated cellulose or an acid-treated cellulose derivative, wherein the acid-treated cellulose or the acid-treated cellulose derivative has been treated with an alkylbenzenesulfonic acid.

Überraschenderweise hat sich gezeigt, dass durch eine Säurebehandlung von Cellulose oder einem Cellulosederivat die Einarbeitbarkeit in eine flüssige Matrix eines Wasch- oder Reinigungsmittel verbessert werden kann, ohne dass die vergrauungsinhibierende Eigenschaft der Cellulose oder des Cellulosederivats verloren geht. Durch die verbesserte Einarbeitbarkeit werden ästhetisch ansprechende flüssige Wasch- oder Reinigungsmittel mit vergrauungsinhibierender Eigenschaft erhalten.Surprisingly, it has been found that the incorporability into a liquid matrix of a washing or cleaning agent can be improved by an acid treatment of cellulose or a cellulose derivative without losing the graying-inhibiting property of the cellulose or of the cellulose derivative. The improved incorporability of aesthetically pleasing liquid detergents or cleaners are obtained with graying-inhibiting property.

Es ist bevorzugt, dass das Mittel ein säurebehandeltes Cellulosederivat ausgewählt aus der Gruppe bestehend aus säurebehandelter Carboxymethylcellulose (CMC), einem säurebehandelten Ethersulfonsäuresalz von Cellulose, einem säurebehandelten sauren Schwefelsäureestersalz von Cellulose, säurebehandelter Methylcellulose, säurebehandelter Ethylcellulose, säurebehandelter Hydroxyethylcellulose, säurebehandelter Hydroxypropylcellulose, säurebehandelter Hydroxypropylmethylcellulose, säurebehandelter Methylhydroxyethylcellulose, säurebehandelter Methylcarboxymethylcellulose, säurebehandelter Ethylhydroxyethylcellulose und einer Mischung dieser säurebehandelten Cellulosederivate enthält.It is preferred that the agent is an acid-treated cellulose derivative selected from the group consisting of acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid ester salt, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose and a mixture of these acid-treated cellulose derivatives.

Diese säurebehandelten Cellulosederivate lassen sich besonders stabil und gleichmäßig in die flüssige Matrix eines Wasch- oder Reinigungsmittels einarbeiten.These acid-treated cellulose derivatives can be incorporated in a particularly stable and uniform manner in the liquid matrix of a washing or cleaning agent.

Dabei ist es insbesondere bevorzugt, dass das säurebehandelte Cellulosederivat säurebehandelte Carboxymethylcellulose (CMC) und/oder säurebehandelte Hydroxypropylmethylcellulose ist. Insbesondere bevorzugt ist die säurebehandelte Carboxymethylcellulose säurebehandelte Natriumcarboxymethylcellulose.In this case, it is particularly preferred that the acid-treated cellulose derivative is acid-treated carboxymethylcellulose (CMC) and / or acid-treated hydroxypropylmethylcellulose. Particularly preferred is the acid-treated carboxymethyl cellulose acid-treated sodium carboxymethyl cellulose.

Diese säurebehandelten Cellulosederivate weisen besonders hohe vergrauungsinhibierende Eigenschaften auf und führen nach ihrer Einarbeitung in die flüssige Matrix von Wasch- oder Reinigungsmitteln zu transparenten Produkten ohne Agglomerate, Ausfällungen des Cellulosederivats.These acid-treated cellulose derivatives have particularly high graying-inhibiting properties and, after incorporation into the liquid matrix of detergents or cleaners, lead to transparent products without agglomerates and precipitates of the cellulose derivative.

Es ist bevorzugt, dass die Menge an säurebehandelter Cellulose oder säurebehandeltem Cellulosederivat 0,01 bis 10 Gew.-% und mehr bevorzugt 0,1 bis 8 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, beträgt.It is preferred that the amount of acid-treated cellulose or acid-treated cellulose derivative is from 0.01% to 10% by weight, and more preferably from 0.1% to 8% by weight, based on the total liquid detergent or cleaning agent.

Diese Mengen an Cellulose oder Cellulosederivat haben sich als besonders vorteilhaft erwiesen. Unter einer Menge von 0,01 Gew.-% kann kein vergrauungsinhibierender Effekt beobachtet werden und bei Mengen größer 8 Gew.-% kann keine weitere Steigerung der vergrauungsinhibierenden Wirkung des flüssigen Wasch- oder Reinigungsmittels beobachtet werden.These amounts of cellulose or cellulose derivative have proven to be particularly advantageous. At a level of 0.01% by weight, no graying-inhibiting effect can be observed, and at amounts greater than 8% by weight, no further increase in the graying-inhibiting effect of the liquid detergent or cleaning agent can be observed.

Die säurebehandelte Cellulose oder das säurebehandelte Cellulosederivat sind mit einer Alkylbenzolsulfonsäure behandelt worden. Die Salze von Alkylbenzolsulfonsäure sind häufig verwendete anionische Tenside in flüssigen Wasch- oder Reinigungsmitteln. Durch den Einsatz von Alkylbenzolsulfonsäure als Säure in der Säurebehandlung braucht einerseits keine zusätzlich Chemikalie verwendet werden und die säurebehandelte Cellulose oder das säurebehandelte Cellulosederivat kann direkt, dass heißt ohne weitere Aufarbeitung, in der Herstellung des flüssigen Wasch- oder Reinigungsmittels eingesetzt werden. Dies macht die Herstellung des flüssigen Wasch- oder Reinigungsmittels besonders effektiv.The acid-treated cellulose or the acid-treated cellulose derivative has been treated with an alkylbenzene sulfonic acid. The salts of alkylbenzenesulfonic acid are commonly used anionic surfactants in liquid detergents or cleaners. By using alkylbenzenesulfonic acid as the acid in the acid treatment, on the one hand, no additional chemical must be used and the acid-treated cellulose or the acid-treated cellulose derivative can be used directly, ie without further workup, in the preparation of the liquid detergent or cleaning agent be used. This makes the preparation of the liquid detergent or cleaning agent particularly effective.

Ferner betrifft die Erfindung die Verwendung einer entsprechend säurebehandelten Cellulose oder eines entsprechend säurebehandelten Cellulosederivats in einem flüssigen Wasch- oder Reinigungsmittel zur Erhöhung der Anti-Vergrauungsleistung des Wasch- oder Reinigungsmittels.Furthermore, the invention relates to the use of a correspondingly acid-treated cellulose or a corresponding acid-treated cellulose derivative in a liquid washing or cleaning agent to increase the anti-graying performance of the washing or cleaning agent.

In einem weiteren Aspekt betrifft die Erfindung ein Verfahren zur Herstellung eines flüssigen Wasch- oder Reinigungsmittels, enthaltend 1 bis 70 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel Tensid(e) und eine säurebehandelte Cellulose oder ein säurebehandeltes Cellulosederivat, bei dem

  1. a) eine Cellulose oder ein Cellulosederivat mit einer Alkylbenzolsulfonsäure vermahlen wird und
  2. b) die erhaltene gemahlene Mischung mit den Tensiden und den weiteren Bestandteilen des Wasch- oder Reinigungsmittels gemischt wird.
In a further aspect, the invention relates to a process for the preparation of a liquid washing or cleaning agent containing 1 to 70 wt .-%, based on the total liquid detergent or detergent surfactant (s) and an acid-treated cellulose or an acid-treated cellulose derivative, at the
  1. a) a cellulose or a cellulose derivative is ground with an alkylbenzenesulfonic acid, and
  2. b) the resulting ground mixture is mixed with the surfactants and the further constituents of the washing or cleaning agent.

In noch einem weiteren Aspekt betrifft die Erfindung ein Verfahren zur Herstellung eines flüssigen Wasch- oder Reinigungsmittels, enthaltend 1 bis 70 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel Tensid(e) und eine säurebehandelte Cellulose oder ein säurebehandeltes Cellulosederivat, bei dem

  1. a) eine Cellulose oder ein Cellulosederivat mit einer wässrigen Lösung einer Alkylbenzolsulfonsäure unter Rühren in Kontakt gebracht wird und
  2. b) die erhaltene Mischung mit den Tensiden und den weiteren Bestandteilen des Wasch- oder Reinigungsmittels gemischt wird.
In a still further aspect, the invention relates to a process for the preparation of a liquid washing or cleaning composition containing from 1 to 70% by weight, based on the total liquid detergent or cleaning agent, of surfactant (s) and an acid-treated cellulose or an acid-treated cellulose derivative, in which
  1. a) a cellulose or a cellulose derivative is brought into contact with an aqueous solution of an alkylbenzenesulfonic acid with stirring, and
  2. b) the mixture obtained is mixed with the surfactants and the further constituents of the washing or cleaning agent.

Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, eingehender erläutert werden.In the following, the invention will be explained in more detail, inter alia, by way of examples.

Das flüssige Wasch- oder Reinigungsmittel enthält eine säurebehandelte Cellulose oder ein säurebehandeltes Cellulosederivat, die jeweils mit einer Alkylbenzolsulfonsäure behandelt worden sind. Das entsprechend säurebehandelte Cellulosederivat ist vorzugsweise säurebehandelte Carboxymethylcellulose (CMC), ein säurebehandeltes Ethersulfonsäuresalz von Cellulose, ein säurebehandeltes saures Schwefelsäureestersalz von Cellulose, säurebehandelte Methylcellulose, säurebehandelte Ethylcellulose, säurebehandelte Hydroxyethylcellulose, säurebehandelte Hydroxypropylcellulose, säurebehandelte Hydroxypropylmethylcellulose, säurebehandelte Methylhydroxyethylcellulose, säurebehandelte Methylcarboxymethylcellulose, säurebehandelte Ethylhydroxyethylcellulose oder eine Mischung dieser säurebehandelten Cellulosederivate. Ganz besonders bevorzugt ist das Cellulosederivat säurebehandelte Carboxymethylcellulose, insbesondere säurebehandelte Natriumcarboxymethylcellulose, und/oder säurebehandelte Hydroxypropylmethylcellulose.The liquid washing or cleaning agent contains an acid-treated cellulose or an acid-treated cellulose derivative, each of which has been treated with an alkylbenzenesulfonic acid. The corresponding acid-treated cellulose derivative is preferably acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid salt, acid-treated cellulose acid acid sulfate, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose or the like Mixture of these acid-treated cellulose derivatives. Very particular preference is given to the cellulose derivative acid-treated carboxymethylcellulose, in particular acid-treated sodium carboxymethylcellulose, and / or acid-treated hydroxypropylmethylcellulose.

Die säurebehandelte Cellulose oder das säurebehandelte Cellulosederivat wird mit einer Alkylbenzolsulfonsäure behandelt. Insbesondere bevorzugt wird Dodecylbenzolsulfonsäure und/oder C10-C13-Alkylbenzolsulfonsäure zur Säurebehandlung der Cellulose oder des Cellulosederivats eingesetzt.The acid-treated cellulose or the acid-treated cellulose derivative is treated with an alkylbenzene sulfonic acid. Particular preference is given to using dodecylbenzenesulfonic acid and / or C 10 -C 13 -alkylbenzenesulfonic acid for the acid treatment of the cellulose or of the cellulose derivative.

Die Menge an säurebehandelter Cellulose oder säurebehandeltem Cellulosederivat beträgt vorzugsweise 0,01 bis 10 Gew.-% und mehr bevorzugt 0,1 bis 8 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The amount of acid-treated cellulose or acid-treated cellulose derivative is preferably 0.01 to 10 wt .-%, and more preferably 0.1 to 8 wt .-%, each based on the total liquid detergent or cleaning agent.

In einer Ausführungsform der Erfindung erfolgt die Säurebehandlung der Cellulose oder des Cellulosederivats durch Vermahlen mit einer Alkylbenzolsulfonsäure. Dabei ist es bevorzugt, dass der Vermahlungsprozess in einer Kugelmühle erfolgt. In dieser Ausführungsform ist es vorteilhaft, wenn die Menge an Alkylbenzolsulfonsäure 0,01 bis 50 Gew.-% und mehr bevorzugt 0,1 bis 5 Gew.-%, bezogen auf die gesamte Cellulose(derivat)/ Alkylbenzolsulfonsäure-Mischung, beträgt. Entsprechend ist es auch vorteilhaft, wenn die Menge an Cellulose(derivat) 50 bis 99,99 Gew.-% und mehr bevorzugt 95 bis 99,9 Gew.-%, jeweils bezogen auf die gesamte Cellulose(derivat)/ Alkylbenzolsulfonsäure-Mischung, beträgt.In one embodiment of the invention, the acid treatment of the cellulose or the cellulose derivative is carried out by grinding with an alkylbenzenesulfonic acid. It is preferred that the grinding process takes place in a ball mill. In this embodiment, it is advantageous if the amount of alkylbenzenesulfonic acid is from 0.01 to 50% by weight, and more preferably from 0.1 to 5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture. Accordingly, it is also advantageous if the amount of cellulose (derivative) is 50 to 99.99% by weight and more preferably 95 to 99.9% by weight, in each case based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture, is.

Beim Vermahlungsprozess kann es zur Verbesserung der Prozessierbarkeit von Vorteil sein, dass neben der Cellulose oder dem Cellulosederivat und der Alkylbenzolsulfonsäure ein Lösungsmittel vorhanden ist. Bevorzugt wird Ethanol als Lösungsmittel verwendet. Es ist besonders bevorzugt, Carboxymethylcellulose, insbesondere Natriumcarboxymethylcellulose, mit einer C10-C13-Alkylbenzolsulfonsäure durch Mahlen in einer Kugelmühle zu behandeln.In the milling process, it may be advantageous to improve the processability that a solvent is present in addition to the cellulose or the cellulose derivative and the alkylbenzenesulfonic acid. Preferably, ethanol is used as the solvent. It is particularly preferred to treat carboxymethylcellulose, especially sodium carboxymethylcellulose, with a C 10 -C 13 -alkylbenzenesulfonic acid by ball milling.

Mit C10-C13-Alkylbenzolsulfonsäure vermahlene Natriumcarboxymethylcellulose kann stabil in die Matrix eines flüssigen Wasch- oder Reinigungsmittels eingearbeitet werden, ohne dass es zu Ausfällungen, Aufrahmungen, Ablagerungen und/oder Verklumpungen kommt. Flüssige Waschoder Reinigungsmittel mit einer C10-C13-Alkylbenzolsulfonsäure vermahlenen Natriumcarboxymethylcellulose weisen eine hohe Transparenz und gute vergrauungsinhibierende Eigenschaften auf.Sodium carboxymethylcellulose ground with C 10 -C 13 -alkylbenzenesulfonic acid can be stably incorporated into the matrix of a liquid detergent or cleaning agent without precipitation, creaming, deposits and / or lumps. Liquid detergent or cleaning agent having a C 10 -C 13 alkyl benzene milled sodium carboxymethylcellulose have a high transparency and good graying-inhibiting properties.

In einer weiteren Ausführungsform der Erfindung erfolgt die Säurebehandlung einer Cellulose oder eines Cellulosederivats durch in Kontakt bringen der Cellulose oder des Cellulosederivats mit einer wässrigen Lösung einer Alkylbenzolsulfonsäure unter Rühren. In dieser Ausführungsform ist es vorteilhaft, wenn bei Einsatz einer Alkylbenzolsulfonsäure die Menge an Alkylbenzolsulfonsäure 0,1 bis 20 Gew.-% bezogen auf die gesamte Cellulose(derivat)/ Alkylbenzolsulfonsäure/Wasser-Mischung beträgt. Ferner ist bevorzugt, wenn die Menge an Cellulose(derivat) 0,01 bis 2,5 Gew.-%, bezogen auf die gesamte Cellulose(derivat)/ Alkylbenzolsulfonsäure/Wasser-Mischung, beträgt. Es ist bevorzugt, Hydroxypropylmethylcellulose einer solchen Säurebehandlung mit einer C10-C13-Alkylbenzolsulfonsäure zu unterziehen. Flüssige Wasch- oder Reinigungsmittel mit einer C10-C13-Alkylbenzolsulfonsäure behandelten Hydroxypropylmethylcellulose sind klar und weisen gute vergrauungsinhibierende Eigenschaften auf.In a further embodiment of the invention, the acid treatment of a cellulose or a cellulose derivative is carried out by contacting the cellulose or the cellulose derivative with an aqueous solution of an alkylbenzenesulfonic acid with stirring. In this embodiment, it is advantageous if, when using an alkylbenzenesulfonic acid, the amount of alkylbenzenesulfonic acid is from 0.1 to 20% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture. It is further preferred if the amount of cellulose (derivative) is from 0.01 to 2.5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture. It is preferred to subject hydroxypropylmethylcellulose to such acid treatment with a C 10 -C 13 -alkylbenzenesulfonic acid. Liquid detergents or cleaners with a C 10 -C 13 -alkylbenzenesulfonic acid treated hydroxypropylmethylcellulose are clear and have good graying-inhibiting properties.

Das flüssige Wasch- oder Reinigungsmittel enthält ferner ein Tensid, welches beispielsweise ein anionisches Tensid, ein nichtionisches Tensid, ein zwitterionisches Tensid, ein kationisches Tensid oder eine Mischung daraus sein kann. Bevorzugt enthält das flüssige Wasch- oder Reinigungsmittel anionisches und nichtionisches Tensid.The liquid detergent or cleaning agent further contains a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof. The liquid washing or cleaning agent preferably comprises anionic and nonionic surfactant.

Als anionisches Tensid können vorzugsweise Sulfonate und/oder Sulfate eingesetzt werden.The anionic surfactant used may preferably be sulfonates and / or sulfates.

Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch C12-18-Alkansulfonate und die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren.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. Also suitable are C 12-18 alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate sind geeignete anionische Tenside.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. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Auch Fettalkoholethersulfate, wie die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet.Also, 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.

Weitere geeignete anionische Tenside sind Seifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren, abgeleitete Seifengemische.Other suitable anionic surfactants are 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.

Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium-, Magnesium- oder Ammoniumsalze vorliegen. Geeignete Ammoniumsalze als Gegenionen für die anionischen Tenside sind die protonierten Formen von Cholin, Triethylamin, Monoethanolamin, Triethanolamin oder Methylethylamin.The anionic surfactants including the soaps may be in the form of their sodium, potassium, magnesium or ammonium salts. Suitable ammonium salts as counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or methylethylamine.

Der Gehalt an anionischem Tensid einschließlich Seifen beträgt vorzugsweise 2 bis 40 Gew.-% und mehr bevorzugt 5 bis 30 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The content of anionic surfactant including soaps is preferably from 2 to 40% by weight and more preferably from 5 to 30% by weight, based in each case on the total liquid detergent or cleaning agent.

Geeignete nichtionische Tenside umfassen alkoxylierte Fettalkohole, alkoxylierte Fettsäurealkylester, Fettsäureamide, alkoxylierte Fettsäureamide, Polyhydroxyfettsäureamide, Alkylphenolpolyglycolether, Aminoxide, Alkylpolyglucoside und Mischungen daraus.Suitable nonionic surfactants include alkoxylated fatty alcohols, 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.

Als nichtionisches Tensid werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 5 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 5 EO oder 7 EO und Mischungen aus diesen. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Geeignet sind ferner auch eine Mischung aus einem (stärker) verzweigten ethoxylierten Fettalkohol und einem unverzweigten ethoxylierten Fettalkohol, wie beispielsweise eine Mischung aus einem C16-18-Fettalkohol mit 7 EO und 2-Propylheptanol mit 7 EO. Insbesondere bevorzugt enthält das Wasch-, Reinigungs-, Nachbehandlungs- oder Waschhilfsmittel einen C12-18-Fettalkohol mit 7 EO oder einen C13-15-Oxoalkohol mit 7 EO oder 8 EO als nichtionisches Tensid.The nonionic surfactant used is 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 can 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. In particular, however, 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). In addition to these nonionic surfactants, 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. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. In particular, the washing, cleaning, after-treatment or washing assistant particularly preferably contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO or 8 EO as nonionic surfactant.

Der Gehalt an nichtionischem Tensid beträgt vorzugsweise 1 bis 40 Gew.-% und mehr bevorzugt 2 bis 30 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The content of nonionic surfactant is preferably 1 to 40 wt .-% and more preferably 2 to 30 wt .-%, each based on the total liquid detergent or cleaning agent.

Die Gesamtmenge an anionischem und nichtionischem Tensid in dem flüssigen Wasch- oder Reinigungsmittel beträgt bis zu 70 Gew.-%, vorzugsweise bis zu 50 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of anionic and nonionic surfactant in the liquid washing or cleaning agent is up to 70 wt .-%, preferably up to 50 wt .-%, based on the total liquid detergent or cleaning agent.

Zusätzlich zu der säurebehandelten Cellulose oder dem säurebehandelten Cellulosederivat und dem/den Tensid(en) kann das flüssige Wasch- oder Reinigungsmittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Wasch- oder Reinigungsmittels weiter verbessern. Im Rahmen der vorliegenden Erfindung enthält das Waschoder Reinigungsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichkatalysatoren, Bleichaktivatoren, Enzyme, Enzymstabilisatoren, Elektrolyte, pH-Stellmittel, Parfüme, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Hautpflegende Wirkstoffe, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber.In addition to the acid-treated cellulose or the acid-treated cellulose derivative and / the surfactant (s), the liquid detergent or cleaning agent may contain other ingredients that the performance and / or aesthetic properties of the washing or cleaning Cleaner further improve. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, enzyme stabilizers, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , 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, skincare active ingredients, swelling and anti-slip agents, softening components and UV absorbers.

Besonders bevorzugte Stoffe, die in dem Wasch- oder Reinigungsmittel enthalten sein können, sind Gerüststoffe, Schauminhibitoren, Enzyme, Parfüme, Fluoreszenzmittel, Farbstoffe, Enzymstabilisatoren und Mischungen daraus. Geeignete Enzyme, die in dem Wasch- oder Reinigungsmittel enthalten sein können, sind beispielsweise Cellulasen, Amylasen, Proteasen, Lipasen, Mannanasen, Pektatlyasen oder Xyloglucanasen. Eine besonders gute Anti-Vergrauungsleistung des Wasch- oder Reinigungsmittels wird erzielt, wenn das Wasch- oder Reinigungsmittel eine Cellulase enthält.Particularly preferred substances which may be included in the washing or cleaning agent are builders, foam inhibitors, enzymes, perfumes, fluorescers, dyes, enzyme stabilizers and mixtures thereof. Suitable enzymes which may be present in the washing or cleaning agent are, for example, cellulases, amylases, proteases, lipases, mannanases, pectate lyases or xyloglucanases. A particularly good anti-graying performance of the washing or cleaning agent is achieved if the washing or cleaning agent contains a cellulase.

Die Wasch- oder Reinigungsmittel sind flüssig und können Wasser als Hauptlösungsmittel enthalten. Alternativ oder zusätzlich zu dem Wasser können die Wasch- oder Reinigungsmittel nichtwässrige Lösungsmittel enthalten.The detergents or cleaners are liquid and may contain water as the main solvent. Alternatively, or in addition to the water, the detergents or cleaners may contain non-aqueous solvents.

Die erfindungsgemäßen Wasch- oder Reinigungsmittel können zum Waschen und/oder Reinigen von textilen Flächengebilden, verwendet werden.The washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics.

Die flüssigen Wasch- oder Reinigungsmittel mit einer säurebehandelten Cellulose oder einem säurebehandelten Cellulosederivat können insbesondere zur Erhöhung der Anti-Vergrauungsleistung des Wasch- oder Reinigungsmittels während des Waschens und/oder Reinigens von textilen Flächengebilden verwendet werden.The liquid washing or cleaning agents with an acid-treated cellulose or an acid-treated cellulose derivative can be used in particular for increasing the anti-graying performance of the washing or cleaning agent during the washing and / or cleaning of textile fabrics.

Eine Möglichkeit zur Herstellung des Wasch- oder Reinigungsmittels beinhaltet, dass zunächst die Cellulose oder das Cellulosederivat mit der Alkylbenzolsulfonsäure vermahlen wird. Anschließend wird die erhaltene Mischung in einen Rührkessel überführt und Wasser, nichtwässrige Lösungsmittel und die weiteren Tenside, falls jeweils vorhanden, zugegeben. Dann wird, falls vorhanden, die Fettsäure zugegeben und es erfolgt die Verseifung des Fettsäureanteils bei 50 bis 60 °C. Anschließend werden die weiteren Bestandteile, vorzugsweise portionsweise, hinzugefügt.One possibility for producing the washing or cleaning agent involves first grinding the cellulose or the cellulose derivative with the alkylbenzenesulfonic acid. Subsequently, the resulting mixture is transferred to a stirred tank and water, non-aqueous solvents and the other surfactants, if present, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.

Eine weitere Möglichkeit zur Herstellung des Wasch- oder Reinigungsmittels sieht vor, dass zunächst die Cellulose oder das Cellulosederivat mit einer wässrigen Lösung der Alkylbenzolsulfonsäure unter kräftigem Rühren in einem Rührkessel in Kontakt gebracht wird. Anschließend werden die nichtwässrige Lösungsmittel und die weiteren Tenside, falls jeweils vorhanden, zugegeben. Dann wird, falls vorhanden, die Fettsäure zugegeben und es erfolgt die Verseifung des Fettsäureanteils bei 50 bis 60 °C. Anschließend werden die weiteren Bestandteile, vorzugsweise portionsweise, hinzugefügt.Another possibility for the preparation of the washing or cleaning agent provides that first the cellulose or the cellulose derivative is brought into contact with an aqueous solution of the alkylbenzenesulfonic acid with vigorous stirring in a stirred tank. Subsequently, the non-aqueous solvents and the other surfactants, if any, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.

In der folgenden Tabelle 1 ist die Zusammensetzungen eines erfindungsgemäßen Wasch- oder Reinigungsmittels E1 sowie die Zusammensetzungen von zwei nicht erfindungsgemäßen Waschoder Reinigungsmitteln V1 und V2 gezeigt. Tabelle 1: Flüssige Wasch- oder Reinigungsmittel E1 sowie V1 bis V2 [alle Mengen sind in Gew.-% Aktivstoff, bezogen auf die gesamte Zusammensetzung, angegeben] Gew.-% Inhaltsstoffe E1 V1 V2 C12-C18 ROH (7 EO) 8,4 8,4 8,4 Na-Laurylethersulfat (2 EO) 10,8 10,8 10,8 C12-C18-Fettsäure 4,8 4,8 4,8 lin. C10-C13-Alkylbenzolsulfonsäure 8,4 8,4 8,4 Phosphonsäure 0,5 0,5 0,5 Citronensäure 2,7 2,7 2,7 Borsäure 1,1 1,1 1,1 Ethanol 2 2 2 Natronlauge (50%ig) 5,5 5,5 5,5 Optischer Aufheller 0,08 0,08 0,08 CMC1 -- -- -- CMC2 -- -- -- CMC3 -- -- -- HPMC1 -- 1 -- HPMC2 1 -- -- Parfüm 0,8 0,8 0,8 Farbstoff 0,0001 0,0001 0,0001 Wasser Ad 100 Ad 100 Ad 100 HPMC1 = unbehandelte Hydroxypropylmethylcellulose
HPMC2 = in wässriger Lösung mit linearer C10-C13-Alkylbenzolsulfonsäure behandelte Hydroxypropylmethylcellulose Table 1 below shows the compositions of a washing or cleaning agent E1 according to the invention and the compositions of two washing or cleaning compositions V1 and V2 which are not according to the invention. Table 1: Liquid washing or cleaning agents E1 and V1 to V2 [all amounts are given in% by weight of active ingredient, based on the total composition] Wt .-% ingredients E1 V1 V2 C 12 -C 18 ROH (7 EO) 8.4 8.4 8.4 Na lauryl ether sulfate (2 EO) 10.8 10.8 10.8 C 12 -C 18 fatty acid 4.8 4.8 4.8 lin. C 10 -C 13 -alkylbenzenesulfonic acid 8.4 8.4 8.4 phosphonic 0.5 0.5 0.5 citric acid 2.7 2.7 2.7 boric acid 1.1 1.1 1.1 ethanol 2 2 2 Caustic soda (50%) 5.5 5.5 5.5 Optical brightener 0.08 0.08 0.08 CMC1 - - - CMC2 - - - CMC3 - - - HPMC1 - 1 - HPMC2 1 - - Perfume 0.8 0.8 0.8 dye 0.0001 0.0001 0.0001 water Ad 100 Ad 100 Ad 100 HPMC1 = untreated hydroxypropylmethylcellulose
HPMC2 = hydroxypropylmethylcellulose treated in aqueous solution with linear C 10 -C 13 -alkylbenzenesulfonic acid

Die eingesetzte Hydroxypropylmethylcellulose war Methocel® K 15 M von The Dow Chemical Company.The hydroxypropyl methylcellulose used was Methocel® K 15 M from The Dow Chemical Company.

Die säurebehandelten Cellulosederivate konnten stabil und gleichmäßig in die flüssige Matrix von Wasch- oder Reinigungsmitteln eingearbeitet werden. Das erhaltene flüssige Wasch- oder Reinigungsmittel E1 war ästhetisch deutlich ansprechender als das Vergleichswasch- oderreinigungsmittel V3. Das Wasch- oder Reinigungsmittel E1 wies eine hohe Transparenz auf und das flüssige Wasch- oder Reinigungsmittel E1 war sogar klar. Dagegen zeigten das Wasch- und Reinigungsmittel V3 keine gleichmäßige Verteilung der Cellulosederivate in der flüssigen Matrix, sondern deutlich sichtbare Agglomerate der Cellulosederivate.The acid-treated cellulose derivatives could be incorporated stably and uniformly into the liquid matrix of detergents or cleaners. The resulting liquid washing or cleaning agent E1 was aesthetically much more appealing than the comparison washing or cleaning agent V3. The washing or cleaning agent E1 had a high transparency and the liquid washing or cleaning agent E1 was even clear. In contrast, the washing and cleaning agent V3 showed no uniform distribution of cellulose derivatives in the liquid matrix, but clearly visible agglomerates of cellulose derivatives.

Das erhaltene flüssige Wasch- oder Reinigungsmittel E1 war auch nach 8 Wochen Lagerung unter verschiedensten klimatischen Bedingungen stabil und zeigten optische Homogenität, wobei die Rezeptur E1 sogar klar war.The resulting liquid washing or cleaning agent E1 was stable even after 8 weeks storage under various climatic conditions and showed optical homogeneity, the formulation E1 was even clear.

Claims (8)

  1. A liquid washing or cleaning agent containing:
    (a) 1 to 70 wt.%, based on the total liquid washing or cleaning agent, surfactant(s), and
    (b) an acid-treated cellulose or an acid-treated cellulose derivative, characterized in that the acid-treated cellulose or the acid-treated cellulose derivative have been treated with an alkyl benzene sulfonic acid.
  2. The washing or cleaning agent according to claim 1, characterized in that the agent contains an acid-treated cellulose derivative selected from the group consisting of acid-treated carboxymethyl cellulose (CMC), an acid-treated ether sulfonic acid salt of cellulose, an acid-treated acidic sulfuric acid ester salt of cellulose, acid-treated methyl cellulose, acid-treated ethyl cellulose, acid-treated hydroxyethyl cellulose, acid-treated hydroxypropyl cellulose, acid-treated hydroxypropyl methylcellulose, acid-treated methyl hydroxyethyl cellulose, acid-treated methyl carboxymethyl cellulose, acid-treated ethyl hydroxyethyl cellulose and a mixture of said acid-treated cellulose derivatives.
  3. The washing or cleaning agent according to claim 1 or 2, characterized in that the acid-treated cellulose derivative is acid-treated carboxymethyl cellulose (CMC) and/or acid-treated hydroxypropyl methylcellulose.
  4. The washing or cleaning agent according to claim 3, characterized in that the acid-treated carboxymethyl cellulose is acid-treated sodium carboxymethyl cellulose.
  5. The washing or cleaning agent according to one of claims 1 to 4, characterized in that the amount of acid-treated cellulose or acid-treated cellulose derivative is 0.01 to 10 wt.% and more preferably 0.1 to 8 wt.%, based in each case on the total liquid washing or cleaning agent.
  6. The use of an acid-treated cellulose or an acid-treated cellulose derivative in a liquid washing or cleaning agent for increasing the anti-graying performance of the washing or cleaning agent, characterized in that the acid-treated cellulose or the acid-treated cellulose derivative has been treated with an alkyl benzene sulfonic acid.
  7. A method for preparing a liquid washing or cleaning agent containing 1 to 70 wt.%, based on the total liquid washing or cleaning agent, surfactant(s) and an acid-treated cellulose or an acid-treated cellulose derivative, in which
    a) a cellulose or a cellulose derivative is ground with an alkyl benzene sulfonic acid, and
    b) the ground mixture obtained is mixed with the surfactants and the further components of the washing or cleaning agent.
  8. A method for preparing a liquid washing or cleaning agent containing 1 to 70 wt.%, based on the total liquid washing or cleaning agent, surfactant(s) and an acid-treated cellulose or an acid-treated cellulose derivative, in which
    a) a cellulose or a cellulose derivative is brought into contact, by stirring, with an aqueous solution of an alkyl benzene sulfonic acid, and
    b) the mixture obtained is mixed with the surfactants and the further components of the washing or cleaning agent.
EP13700094.9A 2012-02-10 2013-01-09 Washing or cleaning agent with cellulose or a cellulose derivative Not-in-force EP2812421B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012202043A DE102012202043A1 (en) 2012-02-10 2012-02-10 Washing or cleaning agent with cellulose or a cellulose derivative
PCT/EP2013/050285 WO2013117361A1 (en) 2012-02-10 2013-01-09 Washing or cleaning agent with cellulose or a cellulose derivative

Publications (2)

Publication Number Publication Date
EP2812421A1 EP2812421A1 (en) 2014-12-17
EP2812421B1 true EP2812421B1 (en) 2018-04-11

Family

ID=47522683

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13700094.9A Not-in-force EP2812421B1 (en) 2012-02-10 2013-01-09 Washing or cleaning agent with cellulose or a cellulose derivative

Country Status (4)

Country Link
US (1) US9169457B2 (en)
EP (1) EP2812421B1 (en)
DE (1) DE102012202043A1 (en)
WO (1) WO2013117361A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013226625A1 (en) * 2013-12-19 2015-06-25 Henkel Ag & Co. Kgaa HPMC-containing liquid detergent
DE102014205869A1 (en) 2014-03-28 2015-10-01 Henkel Ag & Co. Kgaa Washing or cleaning agents

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2539451A (en) * 1948-02-27 1951-01-30 Eastman Kodak Co Method of preparing sulfuric acid esters of cellulose
NL83998C (en) * 1952-06-02
DE3163112D1 (en) 1980-12-17 1984-05-17 Unilever Nv Detergent composition with reduced soil-redeposition effect
DE102007021793A1 (en) * 2007-05-07 2008-11-13 Henkel Ag & Co. Kgaa Washing or cleaning agent with polysaccharide

Also Published As

Publication number Publication date
EP2812421A1 (en) 2014-12-17
WO2013117361A1 (en) 2013-08-15
US9169457B2 (en) 2015-10-27
DE102012202043A1 (en) 2013-08-14
US20140349909A1 (en) 2014-11-27

Similar Documents

Publication Publication Date Title
EP2454356B1 (en) Liquid detergent compositon comprising a polymer preventing graying
EP2346973B1 (en) Washing, cleaning, post-treating or auxiliary washing agent containing silver
EP2142630B1 (en) Detergent or cleaning agent comprising polysaccharide
DE102010003206A1 (en) Washing, cleaning or pretreatment agent with increased fat dissolving power
EP2804937B1 (en) Washing, cleaning or pre-treatment agent with increased cleaning power
DE102009027811A1 (en) Liquid washing or cleaning agent with graying-inhibiting polysaccharide
WO2013186170A1 (en) Detergent, cleaning agent, or pretreatment agent having greater cleaning power ii
EP2553077B1 (en) Washing composition for sensitive textiles
EP2812421B1 (en) Washing or cleaning agent with cellulose or a cellulose derivative
DE102012206707A1 (en) Washing, cleaning or rinsing agent with improved foaming behavior
EP2875107A1 (en) Stable, liquid detergent with anti-redeposition action
EP2875108B1 (en) Liquid detergent composition having dye transfer inhibition
WO2014195215A1 (en) Washing, cleaning or pretreatment agent having increased cleaning power iii
EP2723843B1 (en) Use of washing or cleaning agents having increased cleaning performance
WO2015144603A1 (en) Washing or cleaning compositions
DE102010003535A1 (en) Detergent, useful e.g. for cleaning and/or conditioning of textile fabrics, preferably textile fabrics made of wool or silk, comprises anionic surfactant and hydrophobically modified cationic polymer
DE102012222263A1 (en) Removal of greasy soiling
WO2014195216A1 (en) Washing, cleaning or pretreatment agent having increased cleaning power iv
DE102011006147A1 (en) Washing composition, useful e.g. to reduce tendency to shrink during cleaning and conditioning of textile fabrics, preferably textile fabrics from wool and/or silk, comprises anionic surfactant and hydrophobically modified cationic polymer
DE102010043896A1 (en) Use of in situ prepared zinc soap as pearlescent donor agents in liquid, paste, gel-form to cut-resistant agent, preferably detergents or cleaning agents
DE102013204579A1 (en) Liquid detergent containing long-chain fatty acid soaps

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: 20140314

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

AX Request for extension of the european patent

Extension state: BA ME

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: 20170208

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 17/00 20060101ALI20171006BHEP

Ipc: C11D 3/00 20060101ALI20171006BHEP

Ipc: C11D 3/22 20060101AFI20171006BHEP

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: 20171127

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

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 988030

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180415

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: 502013009886

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180411

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: 20180411

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

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: 20180411

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: 20180411

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: 20180411

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: 20180711

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: 20180411

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: 20180411

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: 20180411

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: 20180711

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

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: 20180411

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: 20180712

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: 20180411

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: 20180411

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

Ref country code: PT

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

Effective date: 20180813

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013009886

Country of ref document: DE

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

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: 20180411

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: 20180411

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: 20180411

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: 20180411

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: 20180411

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Effective date: 20180411

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: 20180411

26N No opposition filed

Effective date: 20190114

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

Ref country code: DE

Payment date: 20190123

Year of fee payment: 7

Ref country code: FR

Payment date: 20190124

Year of fee payment: 7

Ref country code: GB

Payment date: 20190121

Year of fee payment: 7

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

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: 20180411

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

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: 20180411

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: LU

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

Effective date: 20190109

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190131

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: BE

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

Effective date: 20190131

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: 20190131

Ref country code: CH

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

Effective date: 20190131

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: 20190109

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 988030

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190109

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: 20180411

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: 20190109

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

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: 20180411

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013009886

Country of ref document: DE

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

Effective date: 20200109

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

Ref country code: GB

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

Effective date: 20200109

Ref country code: DE

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

Effective date: 20200801

Ref country code: FR

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

Effective date: 20200131

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

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: 20180411

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

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: 20180811

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: 20130109

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

Ref country code: MK

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: 20180411