EP3420061A1 - Mélanges tensioactifs-enzymes optimisés - Google Patents

Mélanges tensioactifs-enzymes optimisés

Info

Publication number
EP3420061A1
EP3420061A1 EP17706204.9A EP17706204A EP3420061A1 EP 3420061 A1 EP3420061 A1 EP 3420061A1 EP 17706204 A EP17706204 A EP 17706204A EP 3420061 A1 EP3420061 A1 EP 3420061A1
Authority
EP
European Patent Office
Prior art keywords
surfactants
surfactant
weight
given
agent
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.)
Withdrawn
Application number
EP17706204.9A
Other languages
German (de)
English (en)
Inventor
Michael Dreja
Hendrik Hellmuth
Alexander Schulz
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 EP3420061A1 publication Critical patent/EP3420061A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • 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
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D1/66—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
    • C11D1/75—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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention is in the field of enzyme technology, in particular the optimization of surfactant-enzyme mixtures, as used for example in detergents or cleaners.
  • the invention relates to an agent, in particular a washing or cleaning agent, which contains at least one enzyme and a specific surfactant mixture.
  • the present invention relates to a method for the cleaning of textiles or hard surfaces and the use of the agent according to the invention for the removal of stains.
  • Typical surfactants used are the petrochemically based LAS (linear alkylbenzenesulfonate) or SAS (secondary alkyl sulfonate) or MES (methyl ester sulfonate), as well as petro- or oleochemically derived nonionic surfactants such as fatty alcohol ethoxylates or amine oxides. Furthermore, e.g. Betaine, amino acid-based surfactants or biosurfactants are used. As enzymes usually hydrolases are used, i.
  • Proteases amylases, lipases, mannanases, pectins, cellulases etc.
  • the stability during storage and the cleaning performance when used in a detergent or cleaning agent depend significantly on the mixture of the individual components. Therefore, an optimized combination of surfactants / surfactant mixtures on the one hand and enzymes / enzyme mixtures on the other hand is necessary for optimized stability and cleaning performance of the individual ingredients.
  • a first subject of the present invention is therefore an agent, in particular washing or cleaning agent, containing
  • the surfactant mixture contains at least one nonionic and at least one anionic surfactant
  • the surfactant mixture contains less than 10% by weight of surfactants based on the total weight of the agent containing an aromatic hydrocarbon moiety and / or a carboxylate moiety, and
  • Xi corresponds to the total number of aliphatic hydrocarbon structural units of all surfactants
  • X2 corresponds to the total number of aromatic hydrocarbon structural units of all surfactants
  • X3 corresponds to the total number of ethylene oxide structural units of all surfactants
  • X4 corresponds to the total number of sulf (on) at structural units (SO3 " / SOv) of all surfactants
  • MTP ATP STP
  • an agent according to the invention for the removal of stains.
  • the present invention is also directed to a process for the cleaning of textiles or hard surfaces, in which an agent according to the invention is used.
  • At least one means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the indication refers to the kind of the ingredient and not to the absolute number of molecules, together with weight data, refers to all compounds of the type indicated, which are contained in the composition / mixture, ie that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.
  • Substantially free of or “free of” as used herein means that the subject ingredient is contained in the corresponding phase or agent in a negligible amount, especially in an amount that is insufficient for the typical functionality of the ingredient is.
  • An object of the invention is an agent, in particular a washing or cleaning agent, which is characterized in that it contains an enzyme and a surfactant mixture, as defined herein in each case.
  • This invention includes all conceivable types of detergents or cleaners, both concentrates and undiluted agents to be used on a commercial scale, in the washing machine or in the hand wash or
  • washing and cleaning agents include washing aids, which in manual or automatic textile washing to the actual washing be metered in to achieve another effect.
  • laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling, and also agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge.
  • textile pre-treatment and post-treatment agents ie those agents with which the laundry item is brought into contact before the actual laundry, for example to dissolve stubborn soiling
  • agents which are in one of the actual Textile laundry downstream step to give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge.
  • the fabric softeners are calculated.
  • compositions according to the invention contain at least one enzyme.
  • the enzyme may be a hydrolytic enzyme or other enzyme in a concentration effective for the effectiveness of the agent.
  • One embodiment of the invention thus represents agents comprising one or more enzymes.
  • Preferred enzymes are all enzymes which can display catalytic activity in the composition according to the invention, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ⁇ -glucosidase, pectinase, carrageenase, perhydrolase, oxidase , Oxidoreductase or a lipase, and mixtures thereof.
  • Enzymes are advantageously contained in the agent in each case in an amount of 1 ⁇ 10 8 to 5 wt .-% based on active protein. More preferably, each enzyme is in an amount of 1 x 10 7 -3 wt%, from 0.00001-1 wt%, from 0.00005-0.5 wt%, from 0.0001 to 0 , 1 wt .-% and particularly preferably from 0.0001 to 0.05 wt .-% in agents according to the invention, based on active protein. Particularly preferably, the enzymes show synergistic cleaning performance against certain stains or stains, ie the enzymes contained in the middle composition mutually support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the composition according to the invention.
  • the amylase (s) is preferably an ⁇ -amylase.
  • the hemicellulase is preferably a pectinase, a pullulanase and / or a mannanase.
  • the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydroase.
  • the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
  • the proteases used are preferably alkaline serine proteases. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are located inside peptides or proteins and thereby cause degradation of proteinaceous soils on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range.
  • the enzyme present in the composition of the invention is a protease.
  • the enzymes employed herein may be naturally occurring enzymes or enzymes modified by naturally occurring enzymes through one or more mutations to positively affect desired properties such as catalytic activity, stability or disinfecting performance.
  • the enzyme is present in the form of an enzyme product in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, in the composition of the invention relative to the total weight of the composition.
  • the active protein content is preferably in the range of 0.00001 to 1 wt .-%, in particular 0.0001 to 0.2 wt .-% based on the total weight of the composition.
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • the determination of the active protein concentration takes place via a titration of the active sites using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (compare M. Bender et al., J. Am. Chem. Soc , 24 (1966), pp. 5890-5913).
  • PMSF phenylmethylsulfonyl fluoride
  • the enzymes to be used may also be formulated together with adjuncts, such as from fermentation.
  • the enzymes are preferably used as enzyme liquid formulation (s).
  • the enzymes are usually not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. advantageously, are such granules, for example,
  • the agent according to the invention may comprise one or more enzyme stabilizers.
  • surfactants present in the surfactant mixture are in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • the surfactant mixture contained in the agent according to the invention comprises at least one surfactant from the group of anionic surfactants and at least one surfactant from the group of nonionic surfactants. Further, the surfactant mixture contains less than 10% by weight of surfactants (based on the total weight of the composition) with aromatic hydrocarbon moieties, such as phenyl or benzyl groups, as well as surfactants with carboxylate groups, such as soaps.
  • carboxylate or “carboxylate moiety” as used interchangeably herein refers to a group of the formula -COO " .
  • surfactants containing such carboxylate groups are soaps, ie, especially the alkali metal salts of fatty acids such as C10- In general, such carboxylate groups are formed in the deprotonation / neutralization of carboxylic acids.
  • aliphatic hydrocarbon radical or “aliphatic hydrocarbon moiety”, as used interchangeably herein, is for the purposes of the invention any linear, branched or cyclic alkyl, alkenyl or alkynyl group.
  • an "ethylene oxide structural unit” is a group described by the following formula: -CH 2 CH 2 -O- If a plurality of ethylene oxide units are present, ie the structural unit has the formula - (CH 2 CH 2 -O) n -, where n is an integer, typically from 1 to 50, each of the units for the purpose of determining whether or not the invention is Condition is met, counted separately.
  • a surfactant with 2 EO, ie - (CH 2 CH 2 -O) 2- has 2 ethylenoxy structural units in the sense of the invention.
  • a “sulfate moiety” is a group contained in a given molecule, which is described by the following formula: -O-SO3 " .
  • a “sulfonate moiety" is described by the following formula: -SO 3 " .
  • the total number of a given structural unit as used herein refers to the presence of this given structural unit in all surfactants present in the surfactant mixture used. Should this structural unit be e.g. be present twice in a specific surfactant independently of each other, this structural unit is also counted twice for this type of surfactant.
  • the total number of the given structural unit in the surfactant mixture is determined from the sum of the number / amounts of this structural unit in the different surfactant / surfactant populations of the surfactant mixture.
  • a type of surfactant, as used herein, refers to the totality of all molecules having an identical chemical structure.
  • the number / amount of a given moiety in a given surfactant population is abbreviated as MTP.
  • MTP is calculated from the product of the number of repeats of the given moiety in a single surfactant of the given surfactant population and the mole fraction of the given surfactant population in the total amount of the surfactant mixture.
  • the number of repeats of the given moiety in a single surfactant of the given surfactant population is abbreviated to ATP.
  • the mole fraction is defined as the value of the quotient of the amount of substance of the given surfactant population and the total amount of all surfactants of the surfactant mixture.
  • STP the mole fraction
  • Suitable compounds from the class of anionic surfactants are those of the formula (I)
  • R represents a linear or branched unsubstituted alkylaryl group.
  • X stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations X + may be selected from NhV, Mg 2+ , Y 2 Ca 2+ 2 Mn 2+ , and mixtures thereof.
  • Alkylaryl refers to organic radicals consisting of an alkyl radical and an aromatic radical Typical examples of such radicals include but are not limited to alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, Undecylbenzene radicals, dodecylbenzene radicals, tridecylbenzene radicals and the like.
  • such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-1
  • R ' and R " together contain from 9 to 19, preferably from 1 to 15, and in particular from 1 to 13, carbon atoms
  • a particularly preferred representative can be described by the formula A-1a:
  • the compound of formula (I) is preferably the sodium salt of a linear alkyl benzene sulfonate.
  • such surfactants containing aromatic structural units are present in this amount (together with carboxylate group-containing surfactants) in an amount of less than 10% by weight, based on the total weight of the composition.
  • Preferred anionic surfactants are those of the formula (II)
  • R is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and mixtures thereof, with the even number of carbon atoms being preferred.
  • radicals R are derived from C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
  • X stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations X + may be selected from NH 4 + , V 2 ⁇ 2+ , ⁇ 2 Mg 2+ , Y 2 Ca 2+ , Y 2 Mn 2+ , and mixtures thereof.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
  • Other cations X + may be selected from NhV, V 2 Zn 2+ , V 2 Mg 2+ , V 2 Ca 2+ , V 2 Mn 2+ , and mixtures thereof.
  • preferably usable anionic surfactants are the alkyl sulfates of the formula
  • R 2 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred.
  • radicals R 2 are derived from C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -oxo alcohols.
  • X is a monovalent cation or the nth part of an n-valent cation, Preferred are the alkali metal ions and including Na + or K + , with Na + being extremely preferred.
  • Other cations X + may be selected from NH 4 + , V 2 ⁇ 2+ , ⁇ 2 Mg 2+ , Y 2 Ca 2+ , Y 2 Mn 2+ , and mixtures thereof.
  • alkyl ester sulfonates in particular those of the formula IV
  • R is -CH (S0 3 X + ) -C (O) -O-R 2 (IV).
  • R is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical.
  • Preferred radicals R are selected from nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, Heneicosylresten and mixtures thereof, wherein the representatives with odd number of carbon atoms are preferred.
  • R-CH radicals are derived from C 12-18 fatty acids, for example from lauryl, myristyl, cetyl or stearic acid.
  • R 2 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical.
  • X stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations X + may be selected from NhV, V 2 Zn 2+ , V 2 Mg 2+ , Y 2 Ca 2+ , Y 2 Mn 2+ , and mixtures thereof.
  • anionic surfactants are the secondary alkanesulfonates. These have, for example, the formula (V)
  • R is CH (S0 3 X + ) R 2 (V), wherein each of R and R 2 is independently a linear or branched alkyl of 1 to 20 carbon atoms and is a linear or branched chain with the carbon atom to which they are attached. branched alkyl, preferably with 10 to 30 carbon atoms, preferably with 10 to 20 carbon atoms and X + is selected from the group Na + , K + , NH 4 + , / 2 Zn 2+ , / 2 Mg 2+ , / 2 Ca 2+ / 2 Mn 2+, and mixtures thereof, preferably Na +.
  • the at least one secondary alkanesulfonate has the following formula (V-1)
  • m + n is an integer between 7 and 17, preferably 10 to 14 and X + is selected from the group Na + , K + , NH 4 + , Zn 2+ , Mg 2+ , Ca 2+ , Mn 2+ and mixtures thereof, preferably Na + .
  • the at least one secondary alkanesulfonate is secondary Ci4-i7 Natriumalkansulfonat.
  • Such secondary C14-17 sodium alkanesulfonate is sold, for example, by Clariant under the tradename "Hostapur SAS60".
  • Suitable nonionic surfactants are, in particular, fatty alcohol alkoxylates.
  • the compositions therefore contain at least one nonionic surfactant of the formula
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical
  • AO for an ethylene oxide (EO) or propylene oxide (PO) grouping
  • n stands for integers from 1 to 50.
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, no-nadecyl, eicosyl and mixtures thereof, wherein the even number C atoms are preferred.
  • radicals R 3 are derived from C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • the index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.
  • amine oxides are suitable.
  • all amine oxides established for this purpose in the prior art ie compounds having the formula RR 2 R 3 NO, wherein each R, R 2 and R 3 is independently of the others an optionally substituted, for example hydroxy-substituted, C1 -C30 hydrocarbon chain is used.
  • Particularly preferably used amine oxides are those in which R is C 12 -C 18 alkyl and R 2 and R 3 are each independently C 1 -C 4 alkyl, in particular C 12 -C 18 alkyl dimethylamine oxides.
  • Suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl- ⁇ , ⁇ -dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.
  • nonionic surfactants which may be included in the described compositions within the meaning of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides, and alkoxylated alcohols. Such surfactants are known in the art.
  • Suitable alkyl (poly) glycosides are, for example, those of the formula R 2 0- [G] P in which R 2 is a branched or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO _ in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X " , in which R vi to R ix for four identical or different, in particular two long and two short chain, alkyl radicals and X "are an anion, in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the total amount of surfactants i. the surfactant mixture, based on the total weight of the composition 5 to 75 wt .-%, preferably 5 to 35 wt .-%, more preferably 10 to 30 wt .-%.
  • compositions of the invention contain less than 10% by weight of surfactants, based on the total weight of the composition, containing an aromatic hydrocarbon moiety and / or a carboxylate moiety.
  • exemplary aromatic hydrocarbon moieties containing surfactants are the alkylbenzenesulfonates of formula (I) described above.
  • the surfactant mixture contains greater than 10% by weight of surfactants based on the total weight of the surfactant mixture containing an aliphatic hydrocarbon moiety and / or an ethylene oxide moiety.
  • the surfactant mixture contains at least one alkyl ester sulfonate, preferably methyl ester sulfonate, and at least one amine oxide, and optionally at least one alkyl ether, wherein the surfactants are each as defined above.
  • the agent may comprise a surfactant mixture consisting in equal parts of C16-18 methyl ester sulfonate, C12-14 alkyl ethers with 7 EO, and lauryldimethyl amine oxide.
  • the surfactants contain the structural units X1 (C12-14 alkyl radical), X3 (ethylene oxide), X4 (sulfonate) and X5 (amine oxide, dimethyl).
  • X2, and ⁇ are each 0.
  • the agent according to the invention is characterized in that the agent
  • (a) contains 5-75% by weight, preferably 5-35% by weight, surfactants based on the total weight of the composition,
  • Ethoxylated polyethyleneimines are used in particular as dirt-dispersing agents. Suitable ethoxylated polyethyleneimines are known, for example, from US Pat. No. 5,565,145 A.
  • compositions according to the invention may comprise, in addition to the ingredients described above, all known ingredients customary in such compositions, preferably at least one further ingredient being present in the composition.
  • the agents according to the invention may in particular contain builders, bleaches, in particular peroxygen compounds or bleach activators. Furthermore, they may contain water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and / or further auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators, as well as dyes and fragrances, and combinations thereof.
  • a combination of the agent according to the invention with one or more further ingredient (s) is advantageous, since such an agent in preferred embodiments according to the invention has an improved cleaning performance by resulting synergisms.
  • a synergism can be achieved by combining the agent according to the invention with a builder (builder) and / or a peroxygen compound and / or a bleach activator, such a synergism can be achieved.
  • the agent according to the invention is a detergent, more preferably a liquid detergent.
  • the compositions according to the present invention are liquid and contain water as the main solvent, i. they are aqueous agents.
  • the water content of the aqueous composition of the present invention is usually 15 to 70% by weight, preferably 20 to 60% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 50% by weight, in each case based on the total amount of agent.
  • non-aqueous solvents may be added to the composition.
  • Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, ethylglycolmethylether, ethyleneglycolethylether, ethyleneglycolpropylether, ethylene glycolmonon-n-butylether, 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-propano
  • the one or more non-aqueous solvents is usually contained in an amount of 0.1 to 60% by weight, preferably 5 to 60% by weight, more preferably 10 to 30% by weight, based on the total composition.
  • compositions according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the composition.
  • additives for improving the flow and drying behavior for adjusting the viscosity and / or for stabilization
  • other additives and additives customary in detergents and cleaners such as UV stabilizers, pearlescing agents, corrosion inhibitors, preservatives, bitter substances, organic salts , Disinfectants, (structuring) polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and skin feel-improving or nourishing additives.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder (builders).
  • builders which can generally be used are, in particular, the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co) builders and, where there are no ecological prejudices against their use, also the phosphates.
  • the agents are phosphate-free.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • polycarboxylic acids in particular citric acid and sugar acids
  • monomeric and polymeric aminopolycarboxylic acids in particular methylglycinediacetic acid, nitrilotriacetic
  • copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polyphosphates, preferably sodium triphosphate. Crystalline or amorphous alkali metal aluminosilicates can be used in particular as water-insoluble, water-dispersible inorganic builder materials. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both beta- and delta-sodium disilicates Na 2 Si 2 O y H 2 O
  • beta- and delta-sodium disilicates Na 2 Si 2 O y H 2 O
  • amorphous alkali silicates practically anhydrous crystalline alkali metal silicates of the above general formula, in the x is a number from 1, 9 to 2, 1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • compositions according to the invention comprise all solid, powdered, liquid, gelatinous or paste-like administration forms of compositions according to the invention which, if appropriate, may also consist of several phases and may be present in compressed or uncompressed form.
  • the agent can be present as a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l.
  • the solid dosage forms of the composition also include extrudates, granules, tablets or pouches.
  • the agent can also be liquid, gelatinous or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.
  • the agent may be present as a one-component system. Such funds consist of one phase.
  • an agent can also consist of several phases. Such an agent is therefore divided into several components.
  • Another object of the invention is a process for the cleaning of textiles or hard surfaces, which is characterized in that in at least one process step, an inventive agent is applied.
  • Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time, or that the items to be cleaned are otherwise treated with a detergent or a solution or dilution of this product.
  • All conceivable washing or cleaning methods can be enriched in at least one of the method steps to the application of a washing or cleaning agent according to the invention and then represent embodiments of the present invention.
  • All facts, objects and embodiments described for means according to the invention are also on these Subject of the invention applicable. Therefore, reference is made at this point expressly to the disclosure in the appropriate place with the statement that this disclosure also applies to the above inventive method.
  • Alternative embodiments of this subject matter of the invention are also processes for the treatment of textile raw materials or for textile care, in which an agent according to the invention becomes active in at least one process step.
  • the invention also encompasses the use of the stain removal agent described herein.
  • the surfactant-enzyme mixtures contained 1% by weight of the respective surfactant.
  • Stain Removal Efficacy Test Relative change in remission relative to baseline in%; the average was made up of 27 test spots according to the AISE protocol; Testing in Miele W918 washing machine, 60 minutes main wash, 30 ° C, water hardness 16 ° dH, 3.5 kg pre-washed standard cotton textiles as load with ballast dirt.
  • the average stain removal performance of the individual surfactants was measured with a mixture of commercial enzymes (PUR, Stainzyme, Mannaway, Lipex) compared to the average stain removal performance of the individual surfactants without surfactants. From this, the delta-SEM value was determined.
  • the structural chemical building blocks (structural units) of the surfactants could be defined in terms of their contribution to stability and cleaning performance in relative units as follows:
  • X1, X2, X3, X4, X5 and ⁇ represent the multiples (total number) of the structural units of all surfactants.
  • the variants E1-E4 of the agents according to the invention are shown below. (In% by weight).
  • PEI Ethoxylated Polyethyleneimine 12 12 12 12 12 (Sokalan HP 20, BASF) C12-18 fatty acid, Na salt 8 8 8 8
  • Enzymes (amylase, protease, cellulase, 1.5 1.5 1.5 1.5 1.5 1.5 lipase, mannanase, pectate lyase)

Landscapes

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

Abstract

La présente invention a trait au domaine de la technologie des enzymes, en particulier à l'optimisation de mélanges tensioactifs-enzymes, tels que ceux utilisés par exemple dans les produits de lavage ou de nettoyage. L'invention concerne notamment un produit, en particulier un produit de lavage ou de nettoyage, qui contient au moins une enzyme et un mélange spécifique de tensioactifs. La présente invention concerne en outre un procédé de nettoyage de textiles ou de surfaces dures, ainsi que l'utilisation du produit selon l'invention pour éliminer des salissures.
EP17706204.9A 2016-02-24 2017-02-17 Mélanges tensioactifs-enzymes optimisés Withdrawn EP3420061A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016202804.9A DE102016202804A1 (de) 2016-02-24 2016-02-24 Optimierte Tensid-Enzym Mischungen
PCT/EP2017/053630 WO2017144365A1 (fr) 2016-02-24 2017-02-17 Mélanges tensioactifs-enzymes optimisés

Publications (1)

Publication Number Publication Date
EP3420061A1 true EP3420061A1 (fr) 2019-01-02

Family

ID=58094419

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17706204.9A Withdrawn EP3420061A1 (fr) 2016-02-24 2017-02-17 Mélanges tensioactifs-enzymes optimisés

Country Status (4)

Country Link
US (1) US20180362891A1 (fr)
EP (1) EP3420061A1 (fr)
DE (1) DE102016202804A1 (fr)
WO (1) WO2017144365A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017223281A1 (de) * 2017-12-19 2019-06-19 Henkel Ag & Co. Kgaa Reinigugnsmittel enthaltend durch Betain stabilisierte Amylase
WO2019148227A1 (fr) * 2018-01-31 2019-08-08 Claro Products Gmbh Détergent spécial pour linge de lit
CN108315748B (zh) * 2018-02-09 2020-01-07 东莞华拓研磨材料有限公司 一种金属清洗剂及其制备方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
PE6995A1 (es) 1994-05-25 1995-03-20 Procter & Gamble Composicion que comprende un polimero de polialquilenoamina etoxilado propoxilado como agente de separacion de sucio
AR003020A1 (es) * 1995-07-24 1998-05-27 Procter & Gamble Composicion detergente que comprende una amilasa de estabilidad oxidativa aumentada y un sistema surfactante especifico.
EP0756000A1 (fr) * 1995-07-24 1997-01-29 The Procter & Gamble Company Compositions détergentes comprenant une amylase spécifiques et alkylbenzène sulfonate linéaire tensioactif
US6121225A (en) * 1998-12-21 2000-09-19 Condea Vista Company Stable aqueous enzyme compositions
DE10258831A1 (de) * 2002-12-17 2004-07-08 Henkel Kgaa Reinigungsmittel für harte Oberflächen
US20080234165A1 (en) * 2007-03-20 2008-09-25 Rajan Keshav Panandiker Liquid laundry detergent compositions comprising performance boosters
DE102008017103A1 (de) 2008-04-02 2009-10-08 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel enthaltend Proteasen aus Xanthomonas
JP5882991B2 (ja) * 2010-05-14 2016-03-09 ザ サン プロダクツ コーポレーション ポリマー含有洗浄組成物ならびにその生成法および使用法
JP5902622B2 (ja) * 2010-09-10 2016-04-13 ライオン株式会社 液体洗浄剤組成物
WO2013064356A1 (fr) * 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa Produit de lavage ou de nettoyage structuré à limite d'écoulement
WO2013064357A1 (fr) * 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa Produit de lavage ou de nettoyage structuré à limite d'écoulement
ES2564700T3 (es) * 2011-12-20 2016-03-28 Unilever N.V. Detergente de lavado de ropa líquido acuoso isotrópico, que comprende secuestrante
US20150275148A1 (en) * 2012-04-20 2015-10-01 The Sun Products Corporation Liquid detergent compositions
DE102012215833A1 (de) * 2012-09-06 2014-03-06 Henkel Ag & Co. Kgaa Enzymstabilisierende Tensidmischung und flüssige Wasch- oder Reinigungsmittel enthaltend diese
GB2523951B (en) * 2013-01-11 2018-12-05 Lion Corp Liquid detergent
MX2015013670A (es) * 2013-03-28 2016-02-18 Procter & Gamble Composiciones de limpieza que contiene una polieteramina.
CA2910836A1 (fr) * 2013-05-24 2014-11-27 The Procter & Gamble Company Composition de lessive fluide et compacte

Also Published As

Publication number Publication date
DE102016202804A1 (de) 2017-08-24
WO2017144365A1 (fr) 2017-08-31
US20180362891A1 (en) 2018-12-20

Similar Documents

Publication Publication Date Title
EP3638780A1 (fr) Lipase de microbulbifer thermotolerans et son utilisation
EP3638762A1 (fr) Lipase de pseudomonas stutzeri et son utilisation
DE102017214870A1 (de) Verbesserte Pflegeeigenschaften von Polyester Textilien II
EP3408367B1 (fr) Effet antiboulochage amélioré sur des textiles en polyester obtenu au moyen d'une cutinase
EP3420061A1 (fr) Mélanges tensioactifs-enzymes optimisés
DE102016214381A1 (de) Wollwaschmittel enthaltend Transglutaminase
EP3693448B1 (fr) Amélioration de la performance du lavage à l'aide du tensioactif taurate
DE102019207891A1 (de) Schaumstabilisierung durch spezifisches Tensidgemisch
DE102019207890A1 (de) Schaumstabilisierung durch spezifisches Tensidgemisch
EP3670637A1 (fr) Régulation de la viscosité dans les agents de rinçage à la main
WO2017153565A1 (fr) Stabilisation d'enzymes dans des produits de nettoyage contenant des enzymes
DE102017206013A1 (de) Wasch- oder Reinigungsmittel mit verbessertem Schaumverhalten
WO2017153564A1 (fr) Produit de nettoyage contenant un aminoxyde
EP3436559A1 (fr) Détergents vaisselle à efficacité de rinçage améliorée
DE102015225463A1 (de) Wasch- oder Reinigungsmittel mit verbesserter Enzymstabilität
DE102019212972A1 (de) Stabile Handgeschirrspülzusammensetzung mit Bleiche
DE102021106506A1 (de) Schlechtgeruchskontrolle in Reinigungsmitteln
EP3786273A1 (fr) Détergent pour le lavage manuel de la vaisselle comprenant un agent de blanchiment
EP3666871A1 (fr) Détergent ou agent de nettoyage contenant de l'iminodisuccinate et/ou de l'iminotrisuccinate
DE102022116719A1 (de) Verfahren zum Waschen von Textilien bei niedrigen Temperaturen mit Textilwaschmitteln enthaltend amphiphile alkoxylierte Poly(ethylen/propylen)imin Copolymere
DE102019107448A1 (de) Schaumstabilisierung durch spezifisches Tensidgemisch
WO2017144623A1 (fr) Stabilisation de protéase dans des produits de nettoyage contenant de l'alkylbenzène sulfonate
DE102020215131A1 (de) Verwendung eines Geschirrspülmittels zur Erhöhung der Dosiergenauigkeit
EP3578629A1 (fr) Procédé de fabrication d'un agent de lavage ou de nettoyage liquide contenant une solution de substance colorante sans agent conservateur
DE102019219832A1 (de) Selbstentfettendes Handgeschirrspülmittel

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180528

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HELLMUTH, HENDRIK

Inventor name: DREJA, MICHAEL

Inventor name: SCHULZ, ALEXANDER

DAV Request for validation of the european patent (deleted)
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: 20190813

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20200225