EP3833732A1 - Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment - Google Patents

Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

Info

Publication number
EP3833732A1
EP3833732A1 EP19750102.6A EP19750102A EP3833732A1 EP 3833732 A1 EP3833732 A1 EP 3833732A1 EP 19750102 A EP19750102 A EP 19750102A EP 3833732 A1 EP3833732 A1 EP 3833732A1
Authority
EP
European Patent Office
Prior art keywords
radiation
weight
acid
atoms
cleaning
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.)
Pending
Application number
EP19750102.6A
Other languages
German (de)
English (en)
Inventor
Anna KLEMMER
Peter Schmiedel
Bent Rogge
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 EP3833732A1 publication Critical patent/EP3833732A1/fr
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/391Oxygen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • C11D17/0021Aqueous microemulsions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40Specific cleaning or washing processes
    • C11D2111/46Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • Liquid detergents are known in the art and have become increasingly popular with consumers in recent years because they offer a number of advantages over solid detergents. These include the simpler dosing and the generally faster dissolution in the wash liquor. In addition, they are often perceived as safer and less aggressive towards textiles and the environment.
  • Liquid detergents however, have the disadvantage that not all of the ingredients that are established in solid detergents and cleaning agents and that the user trusts in their performance, can be easily incorporated in a stable manner.
  • an effective bleaching system which in solid agents usually consists of a peroxidic bleach and a bleach activator that forms a peroxocarboxylic acid under perhydrolysis conditions, is problematic in liquid agents, because the stability of the bleach activator against hydrolytic attack is usually not adequately guaranteed, especially in aqueous agents can be.
  • the presence of oxidative bleaching agents can adversely affect the stability of other detergent and cleaning agent ingredients, such as dyes or fragrances or enzymes.
  • a further known embodiment of the separation principle consists in enveloping at least one of the problematic ingredients with a protective layer which surrounds the ingredient during the production and storage of the liquid agent and prevents contact with the negatively interacting other ingredients, but breaks open under application conditions and releases the ingredient , so that he can contribute the desired amount to the washing or cleaning result of the agent.
  • concentration differences between the liquid agent and the washing or cleaning liquid are used to dissolve the coating layer only under the conditions in which the agent is used.
  • the present invention uses targeted energy input in order to produce a reactive active ingredient from an ingredient that is stable when the liquid agent is stored.
  • the invention relates to a water and surfactant-containing liquid washing or cleaning agent which contains a hydrophobic precursor compound in microemulsified form, from which a peroxocarboxylic acid or its salt can be released by UV radiation.
  • Such precursor compounds are contained in the agents according to the invention preferably in amounts from 0.1% by weight to 20% by weight, in particular from 1% by weight to 15% by weight.
  • Another object of the invention is the use of a combination of an aqueous microemulsion of a hydrophobic precursor compound, from which a peroxocarboxylic acid or its salt can be released by UV radiation, and UV radiation for removing stains when washing textiles or when cleaning hard surfaces.
  • the microemulsion mentioned here can be a washing or cleaning agent according to the invention, but conventional components of washing and cleaning agents can also be missing;
  • the microemulsion used according to the invention preferably contains from 2% by weight to 12% by weight, in particular from 4% by weight to 10% by weight of the hydrophobic precursor compound, from 2% by weight to 40% by weight, in particular from 4% by weight to 35% by weight of microemulsifier and to 100% by weight of water.
  • Another object of the invention is a washing or cleaning process in which a textile surface in need of washing or a hard surface in need of cleaning is brought into contact with a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which UV- Irradiation a peroxocarboxylic acid or its salt can be released, and UV radiation can act on the liquid.
  • a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form, from which UV- Irradiation a peroxocarboxylic acid or its salt can be released, and UV radiation can act on the liquid.
  • Such a method can be carried out manually or mechanically, for example with the aid of a washing machine or a dishwasher, the washing machine or dishwasher having a device for UV radiation or the washing or cleaning liquid, in particular when the method is carried out manually, using a UV Radiation source is exposed. Washing machines and dishwashers that have a UV radiation source are well
  • the process according to the invention can be carried out at temperatures even below room temperature, in particular when using cold water for preparing the surfactant-containing aqueous washing or cleaning liquid, or is preferably carried out at temperatures in the range from 5 ° C. to 60 ° C., in particular from 10 ° C. up to 40 ° C.
  • UV radiation can act on the liquid shortly before it is brought into contact with the object to be cleaned. It is preferred if the action of UV radiation takes place during the contact of the washing or cleaning liquid with the textile to be washed or the hard surface to be cleaned, the UV radiation not during the entire contact period, which is generally 1 minute to 2 Hours, in particular 2 minutes to 1 hour, must act, but the action can, if desired, begin even before the contact.
  • UV radiation is electromagnetic radiation, which comprises the wavelengths from 100 nm to 380 nm in the spectrum.
  • UV radiation is preferably used which has wavelengths in the range from 100 nm to 300 nm, in particular from 240 nm to 270 nm, it being further preferred if the maximum intensity of the UV radiation is in the range mentioned.
  • the particularly preferred range from 240 nm to 270 nm is in the UVC range and is not covered by sunlight, since its UVC component is filtered out by the atmosphere before reaching the earth's surface.
  • mercury vapor lamps or light-emitting diodes (LEDs) can be used to generate the UV radiation essential to the invention. UV exposure times in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, are normally completely sufficient.
  • Hydrophobic in connection with the precursor compound means that it has an n-octanol / water partition coefficient log K 0 w at 20 ° C. of at least 0.5, preferably in the range from 1 to 30, and in particular from 2 to 20.
  • microemulsified refers to the well-known chemical meaning of the term and indicates that at least one liquid is in another with average droplet diameters in the single-digit to double-digit micrometer range is distributed and the normally immiscible liquids are present without visible segregation.
  • the (o / w) microemulsions preferred according to the invention contain the precursor which is finely divided in water and is stabilized with the aid of a microemulsifier; they are optically isotropic, microstructured and thermodynamically stable.
  • microemulsifiers which can be used include alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides, sulfonates, and in particular alkyl / benzonate sulfonates, mixtures thereof, and / or alkylbenzene sulfonates, mixtures thereof, Alkyl glycol ethers, sulfonates and mixtures thereof are particularly preferred.
  • Such microemulsifiers are contained in the agents according to the invention preferably in amounts of 0.01% by weight to 60% by weight, in particular 1% by weight to 50% by weight.
  • the precursor compounds which can be used according to the invention are obtained in particular from the peroxoesters of one of the general formulas (I) to (VI),
  • R '"(-0 (-A0) -C-00-R) m in which R for a linear or branched chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R ' for a linear or branched chain Alkyl group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R " for a linear or branched chain alkylene group with 1 to 30 C atoms, in particular 2 to 20 C atoms, R"'for an m-bonded linear or branched-chain alkyl group with 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A for an alkylene group with 2 to 4 carbon atoms, m for a number from 2 to 6, in particular 3 or 4, and n for a number and their mixtures are selected from 2 to 30, in particular from 3 to 15.
  • these peroxoesters presumably give rise to free radical intermediate compounds from the action of UV radiation, which compounds directly on the surfaces to be cleaned or in colored stains in the washing or cleaning liquid react or by reaction with water, for example, to form peroxyacids which develop their bleaching performance.
  • Peroxoesters of this type are commercially available under the name Luperox®.
  • Another advantage of the invention is that when such microemulsified hydrophobic precursor compounds are used, the stability of enzymes, for example proteases, in liquid media during storage is just as high as if the precursor compound were dispensed with, whereas the same use of H2O2 or phthalimidoperoxohexanoic acid instead Precursor compound leads to significant decreases in enzyme activity.
  • enzymes for example proteases
  • Liquid when used in relation to the agent according to the invention, includes all compositions which are flowable under standard conditions (20 ° C., 1013 mbar) and in particular also includes gels and pasty compositions. In particular, the term also includes non-Newtonian liquids which have a yield point.
  • the amounts stated in connection with the constituents of the liquid agent described herein relate to% by weight, based on the total weight of the agent, unless stated otherwise.
  • quantities which relate to at least one component always relate to the total amount of this type of component which is contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in combination with at least one nonionic surfactant, refer to the total amount of nonionic surfactants contained in the product.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compositions described herein, this information does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant” therefore means, for example, one or more different nonionic surfactants, that is to say one or more different types of nonionic surfactants. Together with quantity information, the quantity information relates to the total quantity of the correspondingly designated type of constituent, as already defined above.
  • the liquid detergent or cleaning agent according to the present invention preferably contains 1% by weight to 60% by weight, preferably 5% by weight to 45% by weight and, in particular if it is a detergent, 15% by weight. % to 40% by weight of at least one surfactant.
  • Nonionic surfactants include all known nonionic surfactants commonly used in detergents or cleaning agents, especially those selected from the group consisting of alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, Alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides and mixtures thereof.
  • the agents contain at least one fatty alcohol alkoxylate of the formula below as the nonionic surfactant
  • R 1 -0- (AO) mH in which R 1 is a linear or branched, substituted or unsubstituted alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) group and m is an integer from 1 to 50 ,
  • R 1 is a linear or branched alkyl radical having 5 to 30 C atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred , Particularly preferred R 1 radicals are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or oxo alcohols having 10 to 19 carbon atoms.
  • AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • the index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • the agent according to the invention can contain mixtures of nonionic surfactants which have different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred.
  • Such fatty alcohol ethoxylates are available under the trade names Dehydol LT7 ® (BASF SE), Lutensol ® A07 (BASF SE), Lutensol ® M7 (BASF SE) and Neodol ® 45-7 (Shell Chemicals).
  • the fatty alcohol ethoxylates mentioned above preferably have degrees of ethoxylation of at least 5, preferably 7.
  • Such fatty alcohol ethoxylates can be used alone, as mixtures of such fatty alcohol ethoxylates or as mixtures with low-ethoxylated fatty alcohol ethoxylates such as Lutensol ® A03 (BASF) may be used. In such mixtures it is preferred that the fatty alcohol ethoxylates with degrees of ethoxylation of at least 5, preferably 7, at least 50% by weight, preferably at least 75% by weight make up the total amount of fatty alcohol ethoxylates.
  • nonionic surfactants which can be contained in the agents for the purposes of the present invention include, but are not limited to, alkyl (poly) glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters and polyhydroxy fatty acid amides.
  • 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 with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10. These can be contained in the agent for example in amounts of up to 5% by weight.
  • the liquid composition according to the present invention preferably contains 1% by weight to 30% by weight, in particular 2% by weight to 20% by weight and particularly preferably at least 10% by weight of at least one anionic surfactant.
  • the anionic surfactants are preferably surfactants from the group of the sulfonates, in particular alkylbenzenesulfonates and / or secondary alkanesulfonates.
  • the agent according to the invention comprises at least one secondary alkane sulfonate.
  • the at least one secondary alkanesulfonate can be any known secondary alkanesulfonate which is suitable for the purpose according to the invention.
  • the alkanesulfonate further comprises any cation, preferably selected from the group Na + , K + , NFLF, 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and their mixtures, particularly preferably Na + .
  • the corresponding acid can also be used in various embodiments, ie the cation is H + .
  • the at least one secondary alkanesulfonate has the formula R 1 CH (S0 3 X + ) R 2 , where each R 1 and R 2 is independently a linear or branched alkyl having 1 to 20 carbon atoms and forms a linear or branched alkyl group with the carbon atom to which they are attached, preferably having 10 to 30 carbon atoms, preferably having 10 to 20 carbon atoms, and X + is selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2 + and their mixtures, preferably Na + .
  • X + can also be H + in various embodiments.
  • the at least one secondary alkanesulfonate has the formula below
  • M + n is preferably an integer between 7 and 17, preferably 10 to 14 and
  • X + is selected from the group Na + , K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof, preferably Na + .
  • X + can also be H + in various embodiments.
  • the at least one secondary alkanesulfonate is secondary C 14-1 7 sodium alkanesulfonate or the corresponding acid.
  • Such a secondary C14-17 sodium alkane sulfonate is sold, for example, by the Clariant company under the trade name "Hostapur SAS60". At this point, it should be expressly pointed out that the agent described here may contain several secondary alkanesulfonates.
  • the agent described herein contains other anionic surfactants that can be used as an alternative or in addition to the secondary alkanesulfonates.
  • anionic surfactants preferably include alkylbenzenesulfonates.
  • Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
  • R ' and R "are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms.
  • a very particularly preferred representative is sodium dodecylbenzenesulfonate or the corresponding acid (HLAS).
  • Na + can be replaced by a cation selected from K + , NH 4 + , 14 Zn 2+ , 14 Mg 2+ , 14 Ca 2+ , 14 Mn 2+ and mixtures thereof or by H + (corresponding acid) in preferred embodiments the secondary alkanesulfonates and alkylbenzenesulfonates described above are used in combination, in particular in a weight ratio of 2: 1 to 1: 2, preferably 1: 1. It is particularly preferred to use the alkylbenzenesulfonates in the acid form.
  • agents can also contain other anionic surfactants, such as, for example, alkyl ether sulfates. Fatty alcohol ether sulfates of the formula below are preferred
  • AO in the above formula represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group and n is an integer from 1 to 50, preferably from 1 to 20 and preferably from Is 2 to 10.
  • X + is any cation and is preferably selected from the group Na + , K + , NH 4 + , 1 Zn 2+ , 1 Mg 2+ , 1 Ca 2+ , 1 Mn 2 and mixtures thereof, particularly preferably Na + .
  • R 4 is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably with from 7 to 25 carbon atoms and especially with 10 to 19 carbon atoms.
  • R 4 radicals are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, the representatives having an even number of carbon atoms being preferred.
  • Particularly preferred radicals R 4 are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms.
  • the agent can contain mixtures of surfactants which have different degrees of alkoxylation n.
  • the indicated degree of ethoxylation n represents a statistical mean, which can be an integer or a fraction for a specific product.
  • the degrees of alkoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the liquid agent can contain at least one fatty acid.
  • fatty acid refers to branched or unbranched carboxylic acids and their salts, the so-called soaps, having 6 to 22, preferably 12 to 18, carbon atoms.
  • the fatty acid soaps can be in the form of their sodium, Potassium or magnesium or ammonium salts are present. In saponified form, they are preferably in the form of their sodium salts and / or ammonium salts.
  • Amines which can be replaced for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred.
  • the fatty acids are used as such, ie not saponified. They can be dissolved, for example, in one or more components of the composition, preferably the at least one nonionic surfactant, and combined in this dissolved form with the other components of the composition.
  • the fatty acid can be emulsified in the final product.
  • Preferred liquid detergents also contain water as a solvent.
  • the compositions contain 4% by weight to 25% by weight, in particular 6% by weight to 15% by weight, of water; in other embodiments of the invention, the agents contain more than 25% by weight and up to 90% by weight of water, in particular 35% by weight to 65% by weight of water.
  • the liquid compositions can additionally contain one or more non-aqueous, organic solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols, such as diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monoxide -butyl ether, diethylene glycol methyl ether, diethyl englycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol,
  • the non-aqueous solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol and mixtures thereof.
  • the non-aqueous solvent contains 1, 2-propanediol, glycerin or a mixture thereof, very particularly preferably glycerin.
  • the agents according to the invention preferably have a viscosity (Brookfield rotational viscometer; spindle adapted to the viscosity range) in the range from 1 mPa.s to 1000 mPa.s, in particular from 5 mPa.s to 500 mPa.s.
  • An agent according to the invention is also preferably translucent, in particular transparent, that is to say it has no optically perceptible cloudiness.
  • the pH of the liquid detergent according to the invention can be adjusted using conventional pH regulators and is preferably in the range from pH 5 to pH 10, in particular from pH 7 to pH 9; these relate to the pH of a 1% (% by weight) solution of the agent in distilled water at 30 ° C.
  • Suitable pH adjusters include acids and / or alkalis. Suitable acids are organic acids such as acetic acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
  • Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • Volatile alkali can also be used, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.
  • the agent may contain other ingredients that improve its application technology and / or aesthetic properties.
  • the detergent preferably additionally contains one or more substances from the group of enzymes, builders, complexing agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-wrinkle inhibitors, anti-crease agents, color transfer inhibitors. antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, softening components and UV absorbers.
  • the agents preferably contain at least one enzyme.
  • the at least one enzyme can be any enzyme known in the art which can develop a catalytic activity in a washing or cleaning agent and includes, but is not limited to, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin cleaving enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. In principle, these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase® and Savinase® by Novozymes.
  • the protease from Bacillus lentus DSM 5483 is derived from those listed under the name BLAP® Protease variants.
  • proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, which under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, under the trade name Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • the proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.
  • amylases are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents or cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this a-amylase are available from Novozymes under the trade names Duramyl® and TermamyKDultra, from Genencor under the name Purasta DOxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • amyloliquefaciens is sold by Novozymes under the name BAN®, and derived variants from the a-amylase from B. stearothermophilus under the names BSG® and Novamyl®, also from Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Fusion products of all of the molecules mentioned can also be used. In addition, the further developments of the a-amylase from Aspergillus niger and A.
  • Examples of usable lipases or cutinases which are contained in particular because of their triglyceride-cleaving activities are the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or more developed lipases, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases, which were originally isolated from Fusarium solani pisi and Humicola insolens, can also be used.
  • lipases are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available.
  • the Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
  • performance aspects include, in particular, the contributions of cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition or graying inhibition), to avivage (tissue effect) or to the exercise of a "stone washed" effect.
  • EG fungal endoglucanase
  • Novozymes under the trade name Celluzyme®
  • the products Endolase® and Carezyme® which are also available from Novozymes, are based on the 50 kD-EG and 43 kD- EG from H. insolens DSM 1800.
  • Other usable commercial products from this company are Cellusoft®, Renozyme® and Celluclean®, for example the 20 kD-EG from Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® are available, further commercial products from AB Enzymes are Eco nase® and Ecopulp®.
  • cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, where the from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax®.
  • Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra. Variants of these enzymes obtainable by point mutations can also be used according to the invention.
  • Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
  • hemicellulases can be used in particular to remove certain problem soils.
  • these include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes and ⁇ -glucanases.
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
  • Hemicellulases which are particularly preferred according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.
  • pectin-degrading enzymes are within the scope of the present invention also counted enzymes with designations of pectinase, pectate lyase, pectin esterase, Pektindemethoxylase, Pektinmethoxylase, pectin methylesterase, pectase, pectin, Pektinoesterase, Pektinpektylhydrolase, pectin depolymerase, endopolygalacturonase, Pektolase, Pektinhydrolase, pectin polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-
  • suitable enzymes in this regard are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® available from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • the liquid compositions preferably contain the at least one enzyme in total amounts established in the prior art.
  • the at least one enzyme in a total amount of 1 ⁇ 10 8 to 5 wt .-% based on active protein or in a total amount of 0.001 to 3 wt .-%, or 0.01 to 1.5 wt .-% or 0.05 to 1.25% by weight.
  • the stated amounts are to be understood such that each enzyme contained can be contained in the stated amounts.
  • the enzymes are preferably used as liquid enzyme formulation (s).
  • the at least one enzyme that is present in a detergent or cleaning agent supports the cleaning performance of the agent on certain stains or stains.
  • An agent according to the invention particularly preferably contains several enzymes, the enzymes being able to belong to the same or different enzyme classes.
  • the enzymes particularly preferably show synergistic effects with regard to their action against certain soiling or stains, that is to say the enzymes contained in the composition mutually support one another in their performance.
  • Polymers based on terephthalate-PEG can be used in particular as antiredeposition agents.
  • (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.
  • Organic builders are particularly suitable as builders, for example the polycarboxylic acids which can be used in the form of their sodium salts or also as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N, N-diacetic acid (GLDA) and methylglycine-N, N-diacetic acid (MGDA), and mixtures of these .
  • Polymeric polycarboxylates are also suitable as builders.
  • alkali metal salts of polyacrylic acid or polymethacrylic acid for example those with a relative molecular weight of 600 to 750,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn be preferred from this group.
  • Copolymers of polycarboxylates, in particular those of acrylic acid are also suitable Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Soluble builders such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferably used in liquid detergents.
  • the agents can additionally contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta (methylenephosphonate), as builders and complexing agents.
  • phosphonates such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriaminepenta (methylenephosphonate), as builders and complexing agents.
  • the liquid detergents and cleaning agents can be produced in an analogous application by methods known in the prior art. They can be filled in a water-soluble envelope and thus be part of a water-soluble packaging. If the agent is packaged in a water-soluble envelope, it is preferred that the water content is less than 10% by weight, based on the total agent, and that the anionic surfactants are present in the form of their ammonium salts or as free acids.
  • a water-soluble packaging contains a water-soluble envelope. The water-soluble covering is preferably formed by a water-soluble film material. Such water-soluble packaging can be made either by vertical form fill sealing (VFFS) or thermoforming processes.
  • VFFS vertical form fill sealing
  • the thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, filling the composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material and sealing the first and second layers with each other at least around the bulges.
  • the water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures.
  • the sheath can be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different.
  • the water-soluble package, comprising the agent and the water-soluble envelope can have one or more compartments.
  • the liquid agent may be contained in one or more compartments, if any, of the water-soluble enclosure.
  • the amount of liquid agent preferably corresponds to the full or half dose required for a washing or cleaning cycle. It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 g / mol to 1,000,000 g / mol, preferably from 20,000 g / mol to 500,000 g / mol, particularly preferably from 30,000 g / mol to 100,000 g / mol and in particular from 40,000 g / mol to 80,000 g / mol.
  • a film material suitable for producing the water-soluble covering can additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers Polylactic acid, and / or mixtures of the above polymers, may be added.
  • preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.
  • Suitable water-soluble films for use in the wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the name M8630, C8400 or M8900.
  • the water-soluble packaging can have an essentially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.
  • the water-soluble packaging can have one or more chambers for storing one or more agents. If the water-soluble packaging has two or more compartments, at least one compartment contains a liquid agent according to the invention, the further compartments may each contain a solid or a differently composed liquid agent, or the contents of the individual chambers together result in a liquid agent according to the Invention.
  • the same composition, non-microemulsified preparations were used, which like the preparations according to the invention were used with or without UV radiation.
  • white cotton cloths (4 cm x 4 cm) provided with standardized blueberry soiling were each provided with 10 ml of the test formulation and for 15 minutes with a UV-C lamp at a wavelength of 253.7 nm and an energy density of 221 , 4 mJ / cm 2 irradiated at a distance of 3 cm or left in a light-tight box for the same time ("unirradiated").
  • the lobules were rinsed with water, dried and their brightness measured.
  • the table below shows the difference in L values after and before treatment; negative values mean that the soiling has become darker, positive values mean that the soiling is lightened.

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Abstract

La présente invention concerne des détergents ou produits de nettoyage liquides contenant de l'eau et des agents tensioactifs, qui contiennent un composé précurseur hydrophobe sous forme microémulsifiée à partir duquel un acide peroxocarboxylique ou son sel peut être libéré par irradiation UV. L'invention concerne également des procédés de lavage de textiles et de nettoyage de surfaces dures à l'aide de ces composés précurseurs.
EP19750102.6A 2018-08-07 2019-08-01 Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment Pending EP3833732A1 (fr)

Applications Claiming Priority (2)

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DE102018213192.9A DE102018213192A1 (de) 2018-08-07 2018-08-07 Flüssiges bleichmittelvorläuferhaltiges Wasch- oder Reinigungsmittel
PCT/EP2019/070745 WO2020030517A1 (fr) 2018-08-07 2019-08-01 Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

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EP3833732A1 true EP3833732A1 (fr) 2021-06-16

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ATE318298T1 (de) * 1995-03-27 2006-03-15 Procter & Gamble Flussige aktivierte bleichmittelzusammensetzungen
US5681805A (en) * 1995-05-25 1997-10-28 The Clorox Company Liquid peracid precursor colloidal dispersions: microemulsions
JP2000516299A (ja) * 1997-12-22 2000-12-05 ザ、プロクター、エンド、ギャンブル、カンパニー 改良された酸素漂白系
WO2007005471A2 (fr) * 2005-06-29 2007-01-11 Jr Chem, Llc Compositions de peroxyde organique stable
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