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EP3749738B1 - Composition tensioactive viscoélastique solide - Google Patents

Composition tensioactive viscoélastique solide Download PDF

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Publication number
EP3749738B1
EP3749738B1 EP19702201.5A EP19702201A EP3749738B1 EP 3749738 B1 EP3749738 B1 EP 3749738B1 EP 19702201 A EP19702201 A EP 19702201A EP 3749738 B1 EP3749738 B1 EP 3749738B1
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Prior art keywords
group
eine
alkyl group
alkyl
aryl
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German (de)
English (en)
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EP3749738A1 (fr
Inventor
Anna KLEMMER
Peter Schmiedel
Filiz Yapici
Boris Nachtsheim
Dominik Göbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to the technical field of solid surfactant compositions, in particular for the provision of surfactant-containing liquors for textile treatment or for cleaning hard surfaces such as dishes, ceramics, glass, wood or plastic, in particular for cleaning textiles.
  • Solid substrate treatment agents have the advantage that, unlike liquid substrate treatment agents, they do not require any preservatives and the ingredients they contain (such as bleach or enzymes) can be incorporated more stably. Liquid forms are increasingly gaining ground on the market, particularly due to their rapid solubility and the associated rapid availability of the active ingredients they contain.
  • pre-portioned substrate treatment agents such as detergent pouches or dishwasher tablets
  • mechanical substrate treatment and use these products in the form of tablets or in the form of bags (also: pillows or pouches), which are usually filled with at least one liquid composition.
  • the use of liquids has the disadvantage that if there are leaks in the bag of the portion, the liquid composition leaks out.
  • solid molded bodies which have to be dissolved or dispersed in an aqueous medium for application to a substrate
  • the solid dissolves well in water.
  • substrate e.g. the laundry
  • the single-use portion must be able to be worked quickly into the aqueous, liquid liquor. Otherwise, the substrate (e.g. textile) in direct contact with the portion will most likely suffer damage from a permanent overconcentration of the surfactant composition on the substrate. It is therefore an object of the invention to provide solid surfactant compositions, in particular as a single-use portion in the form of a lumpy molded body, which dissolve well in water or can be dispersed therein when in contact with water.
  • Viscoelastic, solid surfactant compositions with a storage modulus of 40,000 to 800,000 Pa are known.
  • the viscoelastic surfactant compositions disclosed therein are liquid-crystalline surfactant phases.
  • the production of the viscoelastic surfactant compositions of the prior art depends on the phase behavior of the surfactants contained in each case, which limits the freedom of formulation with regard to the selection of surfactants and their amounts used.
  • EP 2365051 A1 deals with liquid detergent compositions containing surfactants and a linear di-amido gelling agent.
  • WO 2015/058812 A1 teaches an antiperspirant water-in-oil emulsion in stick form, which contains at least one amido gelling agent as well as various oils, an emulsifier and an antiperspirant active ingredient.
  • a further object was therefore to provide solid surfactant compositions which exhibit viscoelastic behavior regardless of the phase behavior of the surfactants used. Surprisingly, it has been shown that this goal can be achieved by formulating a composition containing at least one surfactant and at least one specific organic compound.
  • a viscoelastic, solid surfactant composition in particular as a washing or cleaning agent
  • the composition has a storage modulus between 10 3 Pa and 10 8 Pa, preferably between 10 4 Pa and 10 8 Pa and a loss modulus (in each case at 20°C, a deformation of 0.1% and a frequency of 1 Hz) and the storage modulus in the frequency range between 10 -3 Hz and 10 2 Hz is at least twice as large as the loss modulus.
  • the composition has a storage modulus in a range from 10 5 Pa to 10 7 Pa.
  • the storage modulus is at least five times greater than the loss modulus, particularly preferably at least ten times greater than the loss modulus (each at 20°C, a deformation of 0.1% and a frequency of 1 Hz).
  • the viscoelastic, solid surfactant composition combines all the advantages of a liquid composition despite its solid form, represents an aesthetic product form with a good dissolution profile in textile treatment and an excellent performance profile on the substrate.
  • the viscoelastic, solid surfactant composition of the present invention is storage-stable and dimensionally stable.
  • the said viscoelastic, solid surfactant composition exhibits almost no syneresis even after long-term storage.
  • a substance e.g. a composition
  • a substance is solid if it is in the solid state at 20°C and 1013 mbar.
  • a substance e.g. a composition
  • a substance is viscoelastic and solid if the storage modulus of the substance at 20°C is greater than the existing loss modulus.
  • the storage modulus and loss modulus are notoriously familiar to the expert (cf. Christopher W. Macosco, "Rheology Principles, Measurements and Applications", VCH, 1994, p. 121 ff . or Gebhard Schramm, "Introduction to Rheology and Rheometry", Düsseldorf, 1995, p. 156 ff . or WO 02/086074 A1 , p. 2, 3rd paragraph to p. 4, end of 1st paragraph).
  • the rheological characterization is carried out within the scope of this invention with a rotational rheometer, for example TA-Instruments, type AR G2, Malvern "Kinexus", using a cone-plate measuring system with a diameter of 40 mm and an opening angle of 2° at a temperature of 20°C. These are shear stress-controlled rheometers. However, the determination can also be carried out with other instruments or measuring geometries with comparable specifications.
  • TA-Instruments for example TA-Instruments, type AR G2, Malvern "Kinexus
  • the storage modulus (abbreviation: G ⁇ ) and the loss modulus (abbreviation: G”) were measured using the equipment described above in an experiment with oscillating deformation.
  • the linear viscoelastic range is first determined in a "stress sweep experiment".
  • the shear stress amplitude is increased at a constant frequency of 1 Hz, for example.
  • the moduli G ⁇ and G" are plotted in a double-logarithmic plot. Either the shear stress amplitude or the (resulting) deformation amplitude can be plotted on the x-axis.
  • the storage modulus G ⁇ is below a certain shear stress amplitude or the deformation amplitude. Deformation amplitude is constant, above which it collapses.
  • the inflection point is conveniently determined by placing tangents on the two curve sections.
  • the corresponding deformation amplitude or shear stress amplitude is usually referred to as "critical deformation” or "critical shear stress”.
  • a frequency ramp is run, e.g. between 0.001 Hz and 100 Hz at a constant deformation amplitude.
  • the deformation amplitude must be selected so that it lies in the linear range, i.e. below the critical deformation mentioned above. In the case of the compositions according to the invention, a deformation amplitude of 0.1% has proven to be suitable.
  • the modules G ⁇ and G" are plotted against the frequency in a double logarithmic plot.
  • a substance e.g. a composition
  • a substance is liquid according to the definition of the invention if it is in the liquid state at 20°C and 1013 mbar.
  • a chemical compound is an organic compound if the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen.
  • a chemical compound is an inorganic compound if the molecule of the chemical compound does not contain a covalent bond between carbon and hydrogen.
  • An "endocyclic double bond” is a double bond in a ring of a cyclic compound. The double bond is thus formed entirely by atoms that form the ring.
  • a compound or a structural unit is "aromatic" if it or a structural fragment thereof satisfies the Hückel rule.
  • the average molecular weights given for polymeric ingredients in this application are - unless explicitly stated otherwise - always weight-average molecular weights M w , which can generally be determined by means of gel permeation chromatography using an RI detector, the measurement being conveniently carried out against an external standard.
  • a "surfactant-containing liquor” in the sense of the invention is a liquid preparation for the treatment of a substrate, obtainable by using a surfactant-containing agent and diluting it with at least one solvent (preferably water).
  • the substrates can be fabrics or textiles (such as clothing) as well as hard surfaces (such as dishes, ceramics, plastic, metal).
  • the surfactant compositions according to the invention are preferably used to provide a surfactant-containing liquor is used in machine cleaning processes, such as those carried out by a washing machine for textiles or a dishwasher.
  • the surfactant compositions according to the invention can preferably also be used as cleaning agents for hard surfaces, such as ceramics, toilets or glass.
  • the surfactant compositions according to the invention can be used in particular as cleaning agents for the toilet.
  • the surfactant-containing liquor is preferably applied here through a toilet basket on the edge of the toilet via the flush or stuck directly to the inner surface of the toilet bowl and distributed via the flush.
  • At least one refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component. "At least one inorganic base” therefore means, for example, one or more different inorganic bases, i.e. one or more different types of inorganic bases. Together with amounts, the amounts refer to the total amount of the correspondingly designated type of component.
  • the range includes the limit values.
  • the viscoelastic, solid surfactant composition according to the invention is preferably transparent or translucent. If a mixture according to the invention has a residual light output (transmission) of at least 20% in the spectral range between 380 nm and 780 nm based on the reference measurement, it is considered transparent within the meaning of the invention.
  • the transparency of the surfactant composition according to the invention can be determined using various methods.
  • the Nephelometric Turbidity Unit (NTU) is often used as a measurement value for transparency. It is a unit used in water treatment, for example, for turbidity measurements, e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for turbid surfactant compositions, whereas low values are determined for clear, transparent surfactant compositions.
  • the turbidimeter type HACH Turbidimeter 2100Q from Hach Company, Loveland, Colorado (USA) is used in conjunction with the calibration substances StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU), all of which can also be ordered from Hach Company.
  • the measurement is carried out in A 10 ml measuring cuvette with cap was filled with the composition to be examined and the measurement was carried out at 20 °C.
  • surfactant compositions have a perceptible cloudiness that is visible to the naked eye within the meaning of the invention. It is therefore preferred if the surfactant compositions according to the invention have an NTU value (at 20°C) of at most 120, more preferably at most 110, more preferably at most 100, particularly preferably at most 80.
  • the transparency of the solid agents according to the invention was determined by a transmission measurement in the visual light spectrum over a wavelength range of 380 nm to 780 nm at 20°C.
  • a reference sample water, fully demineralized
  • the cuvette is then filled with a sample of the surfactant composition according to the invention and measured again.
  • the sample is filled in a liquid state and solidified in the cuvette and then measured.
  • the transparent surfactant composition according to the invention has a transmission (20°C) of particularly preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular of at least 50%, very particularly preferably of at least 60%.
  • the transparent surfactant composition according to the invention has a transmission (at 20°C) of at least 30% (in particular of at least 40%, more preferably of at least 50%, particularly preferably of at least 60%) and an NTU value (at 20°C) of at most 120 (more preferably at most 110, more preferably at most 100, particularly preferably at most 80).
  • the viscoelastic, solid surfactant composition according to the invention contains a total amount of 0.1 to 70% by weight of surfactant based on its total weight.
  • the surfactants used according to the invention are preferably anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants or cationic surfactants.
  • Preferred surfactant compositions contain, based on their total weight, a total amount of 5 to 70% by weight, more preferably from 5 to 65% by weight, more preferably from 5 to 60% by weight, more preferably from 10 to 70% by weight, more preferably from 10 to 60% by weight, more preferably from 15 to 70% by weight, more preferably from 15 to 65% by weight, more preferably from 15 to 60% by weight, particularly preferably from 20 to 70% by weight, more preferably from 20 to 65% by weight, more preferably from 20 to 60% by weight, very particularly preferably from 25 to 70 % by weight, more preferably from 25 to 65 % by weight, more preferably from 25 to 60 % by weight, further preferably from 30 to 70 % by weight, more preferably from 30 to 65 % by weight, more preferably from 30 to 60 % by weight of at least one surfactant.
  • These surfactant compositions are particularly suitable for textile treatment, but especially for use in a washing machine for textile washing. It is again particularly preferred if the
  • Preferred embodiments of a surfactant composition according to the invention as a dishwashing detergent, in particular for use in a dishwasher each contain, based on the weight of the composition, 0.1 to 5.0% by weight, in particular 0.2 to 4.0% by weight, of at least one surfactant.
  • a viscoelastic, solid surfactant composition preferred according to the invention is characterized in that it contains at least one anionic surfactant.
  • Surfactant compositions according to the invention with anionic surfactant are particularly suitable for washing textiles, particularly preferably for use in a washing machine for textile washing.
  • Preferred surfactant compositions that are suitable as dishwashing detergents (particularly for use in a dishwasher) each contain 0 to 1% by weight, in particular 0 to 0.5% by weight, particularly preferably 0 to 0.25% by weight, of anionic surfactant, based on the weight of the composition.
  • anionic surfactant is contained in a total amount of 5 to 70 wt.%, more preferably 5 to 60 wt.%, more preferably 10 to 70 wt.%, in particular 10 to 60 wt.%, particularly preferably 10 to 40 wt.%, further preferably 25 to 40 wt.%.
  • sulfonates and/or sulfates can preferably be used as anionic surfactant.
  • suitable surfactants of the sulfonate type are C 9-13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • estersulfonates for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Particularly preferred surfactant compositions according to the invention in particular textile detergents, contain as anionic surfactant at least one compound of the formula (T-1), in the R' and R" are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y + is a monovalent cation or the n-th part of an n-valent cation (in particular Na + ).
  • Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • Fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO, are also suitable.
  • Suitable anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, as well as soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants and the soaps can be in the form of their sodium, potassium, magnesium or ammonium salts.
  • the anionic surfactants are preferably in the form of their ammonium salts.
  • Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.
  • the surfactant composition according to the invention in particular as a textile detergent, contains an alkylbenzenesulfonic acid neutralized with monoethanolamine, in particular C 9-13 alkylbenzenesulfonic acid, and/or a fatty acid neutralized with monoethanolamine.
  • a preferred surfactant composition of the invention contains at least one anionic surfactant selected from the group consisting of C 8-18 alkylbenzenesulfonates, olefinsulfonates, C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
  • the surfactant composition according to the invention in particular as a washing or cleaning agent, contains at least one nonionic surfactant.
  • the at least one nonionic surfactant can be any known nonionic surfactant suitable for the purpose of the invention.
  • the surfactant composition contains at least one nonionic surfactant.
  • Preferred embodiments of a surfactant composition according to the invention as a dishwashing detergent, in particular for use in a dishwasher each contain, based on the weight of the composition, 0.1 to 5.0% by weight, in particular 0.2 to 4.0% by weight, of at least one nonionic surfactant.
  • Preferred embodiments of a surfactant composition according to the invention as a textile detergent, in particular for use in a washing machine each contain, based on the weight of the composition, 1.0 to 25% by weight, preferably 2.5 to 20.0% by weight, more preferably 5.0 to 18.0% by weight, of at least one nonionic surfactant.
  • the at least one nonionic surfactant can be any known nonionic surfactant suitable for the purpose of the invention.
  • the surfactant compositions described herein contain as nonionic surfactant at least one fatty alcohol alkoxylate having the following formula (T-2), R'-O-(XO) m -H (T-2) where R' is a linear or branched C 8 -C 18 alkyl radical, an aryl radical or alkylaryl radical, XO is independently an ethylene oxide (EO) or propylene oxide (PO) group and m is an integer from 1 to 50.
  • R' is a linear or branched, substituted or unsubstituted alkyl radical.
  • R I is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms.
  • Preferred radicals R' are selected from decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, with the representatives with an even number of carbon atoms being preferred.
  • radicals R' are derived from fatty alcohols with 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 19 carbon atoms.
  • XO of formula (T-2) is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index m of the formula (T-2) is an integer from 1 to 50, preferably 2 to 20 and more preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • the surfactant composition according to the invention may contain mixtures of nonionic surfactants having different degrees of ethoxylation.
  • Such fatty alcohol ethoxylates are available under the sales names Dehydol ® LT7 (BASF), Lutensol ® AO7 (BASF), Lutensol ® M7 (BASF) and Neodol ® 45-7 (Shell Chemicals).
  • the surfactant compositions according to the invention particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, particularly as cleaning agents for machine dishwashing. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-20 alcohol preferably a C 18 alcohol
  • at least 12 moles preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Surfactants that are preferably used come from the group of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants in particular for cleaning agents for machine dishwashing, have proven to be low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units in the context of the present invention.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block from the other groups follows.
  • Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally unbranched, with the linear radicals consisting of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol.
  • Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or 2-methyl-branched or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues.
  • nonionic surfactants are preferred in which R 1 in the above formula is an alkyl residue with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • butylene oxide is particularly suitable as an alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 and R 3 are independently selected from - CH 2 CH 2 -CH 3 and -CH(CH 3 ) 2 are also suitable.
  • non-ionic surfactants that are preferably used, in particular for cleaning agents for machine dishwashing, are non-ionic surfactants of the general formula (T-5) R 1 O(AlkO) x M(OAlk) y OR 2 (T-5) where R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently of one another represent values between 1 and 70; and M represents an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
  • nonionic surfactants of the general formula (T-6) R 1 -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y -CH 2 CH(OH)-R 2 (T-6), where R, R 1 and R 2 independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.
  • R 1 -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y O-CH 2 CH(OH)-R 2 (T-7) in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and R 1 and R 2 independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions with formation of a dihydroxy ether.
  • nonionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes optionally additionally contained in the surfactant compositions according to the invention can be significantly improved.
  • Preferred, in particular for cleaning agents for machine dishwashing are those end-capped poly(oxyalkylated) nonionic surfactants which, according to the following formula (T-10) in addition to a radical R 1 , which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60.
  • Particularly preferred are surfactants of the above formula in which R 1 stands for C 7 to C 13 , n stands for an integer from 16 to 28 and R 2 stands for C 8 to C 12 .
  • surfactants of the formula R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2-hydroxydecyl ethers.
  • nonionic surfactants which can preferably be used, in particular for cleaning agents for machine dishwashing, are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x > 2.
  • the value 3 for x has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.
  • the group of these non-ionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the surfactant composition according to the invention can contain amine oxide as a nonionic surfactant.
  • amine oxides established in the prior art for these purposes, i.e. compounds which have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 is independently an optionally substituted hydrocarbon chain with 1 to 30 carbon atoms, can be used as amine oxide.
  • Particularly preferably used amine oxides are those in which R 1 is alkyl with 12 to 18 carbon atoms and R 2 and R 3 are each independently alkyl with 1 to 4 carbon atoms, in particular alkyldimethylamine oxides with 12 to 18 carbon atoms.
  • Suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide, N-tallowalkyl-N,N-dihydroxyethylamine oxide, myristyl/cetyldimethylamine oxide or lauryldimethylamine oxide.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • compositions of the invention described herein may also contain several of the nonionic surfactants described above.
  • the amounts of the individual surfactant components must of course be selected within the specified quantity ranges of the individual surfactant components in such a way that the specified total amount of surfactant is maintained.
  • the viscoelastic, solid surfactant composition according to the invention (in particular as a textile detergent) contains at least one polyalkoxylated polyamine in addition to the surfactant.
  • the polyalkoxylated polyamine in the context of the present invention and its individual aspects is a polymer with a backbone containing N atoms, which carries polyalkoxy groups on the N atoms.
  • the polyamine has primary amino functions at the ends (terminus and/or side chains) and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions in the interior, so that a linear rather than a branched-chain polyamine is obtained.
  • the ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1.
  • the ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8.
  • the polyamine preferably has an average molecular weight in the range from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 5,000 g/mol.
  • the N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups with 2 to 12 C atoms, in particular 2 to 6 C atoms, whereby not all alkylene groups have to have the same number of C atoms.
  • Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and their Mixtures.
  • Polyamines that carry ethylene groups as the alkylene group are also referred to as polyethyleneimine or PEI.
  • PEI is a particularly preferred polymer according to the invention with an N-atom-containing backbone.
  • the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, whereby not every amino function has to be substituted by alkoxy groups.
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 100, in particular 5 to 50.
  • the alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms and/or polyethoxy groups which are bonded to any propoxy radicals present and to N atoms which do not carry any propoxy groups.
  • Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (EO for short).
  • EO ethylene oxide
  • the polyalkoxylated polyamines containing ethoxy and propoxy groups are preferably accessible by reacting polyamines with propylene oxide (PO for short) and subsequent reaction with ethylene oxide.
  • PO propylene oxide
  • the average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, in particular 5 to 20,
  • the average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 10 to 60, in particular 15 to 30.
  • the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine can be partially or completely etherified with a C 1 - C 10 , in particular C 1 -C 3 , alkyl group.
  • Polyalkoxylated polyamines which are particularly preferred according to the invention can be selected from polyamine reacted with 45EO per primary and secondary amino function, PEI's reacted with 43EO per primary and secondary amino function, PEI's reacted with 15EO + 5PO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function, PEI's reacted with 5PO + 39.5EO per primary and secondary amino function, PEI's reacted with 5PO + 15EO per primary and secondary amino function, PEI's reacted with 10PO + 35EO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function.
  • a particularly preferred alkoxylated polyamine is PEI containing 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine.
  • a further preferred subject of the invention is the use of polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and optionally additionally propylene oxide. If polyalkoxylated polyamines with ethylene oxide and propylene oxide are used, the proportion of propylene oxide in the total amount of alkylene oxide is preferably 2 mol% to 18 mol%, in particular 8 mol% to 15 mol%.
  • the viscoelastic, solid surfactant composition according to the invention preferably additionally contains, based on its weight, polyalkoxylated polyamines in a total amount of 0.5 to 12 wt.%, in particular 5.0 to 9.0 wt.%.
  • the viscoelastic, solid surfactant composition according to the invention in particular as a textile detergent, additionally contains at least one soil-release active ingredient.
  • soil-release active ingredients or, because of their ability to make the treated surface, preferably textiles, dirt-repellent, as “soil repellents".
  • Particularly effective dirt-removing active ingredients due to their chemical similarity to polyester fibers, but which can also have the desired effect on fabrics made of other materials, are copolyesters that contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-removing polyesters of the type mentioned, as well as their use, preferably in detergents for textiles, have been known for a long time.
  • polymers made of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents in the German patent specification DE 28 57 292
  • Polymers with a molecular weight of 15,000 to 50,000 made from ethylene terephthalate and polyethylene oxide terephthalate, where the polyethylene glycol units have molecular weights of 1,000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2:1 to 6:1 can be prepared according to the German laid-open specification EN 33 24 258 used in detergents.
  • the European patent EP066944 relates to textile treatment agents containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP185 427 Methyl or ethyl group-end-capped polyesters with ethylene and/or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil-release polymers are known.
  • the European patent EP241984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units.
  • Polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and/or 3-methoxy-1,2-propylene groups and glycerol units and are substituted with C 1 to C 4 alkyl groups are end-group capped.
  • the European patent specification EP253567 relates to soil-release polymers with a molecular weight of 900 to 9000 made from ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 0.6 to 0.95.
  • polyesters can be obtained, for example, by polycondensation of dialkyl terephthalate, dialkyl 5-sulfoisophthalate, alkylene glycols, optionally polyalkylene glycols (where a, b and/or c > 1) and one-sidedly end-capped polyalkylene glycols (corresponding to unit E-III).
  • a polymeric framework is present and thus the coefficients can assume any value in the given interval as an average value. This value reflects the number-average molecular weight.
  • the structures can contain, for example, 1 to 50 units (EI) per polymer chain.
  • An ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols is suitable as unit (E-II), with preference being given to using the aforementioned.
  • the structures can contain, for example, 1 to 50 units (E-II).
  • the preferred amount of structural unit (E-III) used is that which is necessary to achieve the average molecular weights described below.
  • the invention also allows the use of cross-linked or branched polyester structures. This is expressed by the presence of a cross-linking polyfunctional structural unit (E-IV) with at least three to a maximum of 6 functional groups capable of esterification reactions.
  • Functional groups can be, for example, acid, alcohol, ester, anhydride or epoxy groups. Different functionalities in one molecule are also possible.
  • citric acid malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid.
  • polyhydric alcohols such as pentaerythritol, glycerin, sorbitol and/or trimethylolpropane can be used. They can also be polyvalent aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid (trimesithic acid).
  • the weight fraction of crosslinking monomers can be, for example, up to 10% by weight, in particular up to 5% by weight and particularly preferably up to 3% by weight.
  • the polyesters containing the structural units (EI), (E-II) and (E-III) and optionally (E-IV) generally have number-average molecular weights in the range from 700 to 50,000 g/mol, where the number-average molecular weight can be determined by means of size exclusion chromatography in aqueous solution using calibration with the aid of narrowly distributed polyacrylic acid Na salt standards.
  • the number-average molecular weights are preferably in the range from 800 to 25,000 g/mol, in particular 1,000 to 15,000 g/mol, particularly preferably 1,200 to 12,000 g/mol.
  • solid polyesters which have softening points above 40 °C are preferably used as a component of the particle of the second type; they preferably have a softening point between 50 and 200 °C, particularly preferably between 80 °C and 150 °C and extremely preferably between 100 °C and 120 °C.
  • the polyesters can be synthesized by known methods, for example by first heating the above-mentioned components at normal pressure with the addition of a catalyst and then building up the required molecular weights in a vacuum by distilling off superstoichiometric amounts of the glycols used.
  • the known transesterification and condensation catalysts are suitable for the reaction, such as titanium tetraisopropylate, dibutyltin oxide, alkali or alkaline earth metal alcoholates or antimony trioxide/calcium acetate.
  • titanium tetraisopropylate such as titanium tetraisopropylate, dibutyltin oxide, alkali or alkaline earth metal alcoholates or antimony trioxide/calcium acetate.
  • the viscoelastic, solid surfactant composition according to the invention can additionally contain at least one enzyme as a washing or cleaning agent.
  • all enzymes established in the state of the art for textile treatment can be used in this regard.
  • it is one or more enzymes that can develop a catalytic activity in a surfactant-containing liquor, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, ⁇ -glucosidase, Carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof.
  • Preferred hydrolytic enzymes include in particular proteases, amylases, in particular ⁇ -amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, ⁇ -glucanases, and mixtures thereof.
  • Particularly preferred are proteases, amylases and/or lipases and mixtures thereof and very particularly preferred are proteases.
  • These enzymes are in principle of natural origin; based on the natural molecules, improved variants are available for use in washing or cleaning agents, which are therefore preferably used.
  • subtilisin type those of the subtilisin type are preferred.
  • these are the 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 proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes NS, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ® and Savinase ® by Novozymes.
  • the protease variants known as BLAP ® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, the enzymes available under the trade names Durazym ® , Relase ® , Everlase ® , Nafizym ® , Natalase ® , Kannase ® and Ovozyme ® from Novozymes, the enzymes available under the trade names Purafect ® , Purafect ® OxP, Purafect ® Prime, Excellase ® and Properase ® from Genencor, the enzyme available under the trade name Protosol ® from Advanced Biochemicals Ltd., Thane, India, the enzyme available under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, the enzyme available under the trade names Proleather ® and Protease P ® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • the proteases from Bacillus gibsonii and Bacillus pumilus are also particularly preferred.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which have been improved for use in washing or cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar ® ST. Further developments of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and TermamylOultra, from Genencor under the name Purastar ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ® .
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ® , and derived variants of the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ® , also by Company Novozymes. Also worth mentioning for this purpose are the ⁇ -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.
  • lipases or cutinases which can be used according to the invention, which are included in particular because of their triglyceride-splitting activities, but also in order to produce peracids from suitable precursors in situ, are the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular those with the amino acid exchange D96L. They are sold, for example, by the company 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 be used.
  • Lipases which can also be used are available from the company 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 ® are available.
  • lipases and cutinases from Genencor can be used, the starting enzymes of which were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Lipase ® and Lipomax ® originally sold by Gist-Brocades and the enzymes sold by Meito Sangyo KK, Japan, under the names Lipase MY-30 ® , Lipase OF ® and Lipase PL ® , as well as the product Lumafast ® from Genencor.
  • cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other with regard to their various performance aspects, particularly in portions for textile washing.
  • performance aspects include in particular the contribution of the cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition), to the finishing (fabric effect) or to the exertion of a "stone washed" effect.
  • a useful fungal cellulase preparation rich in endoglucanase (EG) or its further developments is offered by Novozymes under the trade name Celluzyme ® .
  • Endolase ® and Carezyme ® are based on the 50 kD EG and the 43 kD EG from H. insolens DSM 1800 respectively.
  • Other commercial products that can be used This company's products are Cellusoft ® , Renozyme ® and Celluclean ® .
  • Other products that can also be used include the 20 kD EG from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ® and Biotouch ® .
  • Other commercial products from AB Enzymes are Econase ® and Ecopulp ® .
  • Other suitable cellulases are from Bacillus sp.
  • CBS 670.93 and CBS 669.93 whereby the one 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 that can be obtained 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 include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-splitting enzymes and ⁇ -glucanases.
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo ® from the company Novozymes.
  • Hemicellulases that are particularly preferred according to the invention are mannanases, which are sold, for example, under the trade names Mannaway ® by the company Novozymes or Purabrite ® by the company Genencor.
  • the pectin-cleaving enzymes also include enzymes with the names pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methyl esterase, pectin, pectin methyl esterase, pectin esterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endo-polygalacturonase, poly- ⁇ -1,4-galacturonide glycanohydrolase, endogalacturonas
  • Suitable enzymes in this regard are available under the names Gamanase ® , Pektinex AR ® , X-Pect ® or Pectaway ® from the company Novozymes, under the names Rohapect UF ® , Rohapect TPL ® , Rohapect PTE100 ® , Rohapect MPE ® , Rohapect MA plus HC, Rohapect DA12L ® , Rohapect 10L ® , Rohapect B1L ® from the company AB Enzymes and under the name Pyrolase ® from the company Diversa Corp., San Diego, CA, USA.
  • the viscoelastic, solid surfactant composition according to the invention preferably contains enzymes in total amounts of 1 x 10 -8 to 5 percent by weight based on active protein.
  • the enzymes are preferably contained in a total amount of 0.001 to 2% by weight, more preferably 0.01 to 1.5% by weight, even more preferably 0.05 to 1.25% by weight and particularly preferably 0.01 to 0.5% by weight.
  • additional ingredients in the surfactant composition according to the invention as a washing or cleaning agent may include builders, complexing agents, optical brighteners (preferably in textile detergents), pH adjusters, perfume, dye, dye transfer inhibitor or mixtures thereof.
  • builder substances such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids as well as mixtures of these substances, preferably water-soluble builder substances, can be advantageous.
  • phosphates also polyphosphates
  • the viscoelastic, solid surfactant composition according to the invention in this embodiment preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate(s).
  • the surfactant composition according to the invention in this embodiment is particularly preferably completely phosphate-free, i.e. the compositions contain less than 0.1% by weight of phosphate(s).
  • the builders include in particular carbonates, citrates, phosphonates, organic builders and silicates.
  • the weight proportion of the total builders in the total weight of the viscoelastic, solid composition according to the invention is preferably 15 to 80 wt.% and in particular 20 to 70 wt.% for dishwashing detergents.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids which carry more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions in the entire molecule.
  • Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids can also carry other functional groups, such as hydroxyl or amino groups.
  • Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamic N,N-diacetic acid (also known as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.
  • polymeric polycarboxylates organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule
  • polyacetals polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component.
  • these include citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
  • Particularly preferred surfactant compositions according to the invention contain one or more salts of citric acid, i.e. citrates, as one of their essential builders. These are contained in the surfactant compositions according to the invention (in particular for textile washing) preferably in a proportion of 0.3 to 10 wt. %, in particular 0.5 to 8 wt. %, in particular 0.7 to 6.0 wt. %, particularly preferably 0.8 to 5.0 wt. %, in each case based on the total weight of the composition.
  • One or more salts of citric acid are contained in the surfactant compositions according to the invention (in particular for cleaning hard surfaces, in particular for dishwashing) preferably in a proportion of 2 to 40 wt.
  • % in particular 5 to 30 wt. %, in particular 7 to 28 wt. %, particularly preferably 10 to 25 wt. %, very particularly preferably 15 to 20 wt. %, in each case based on the total weight of the composition.
  • the viscoelastic, solid surfactant compositions according to the invention can contain phosphonates in particular as a further builder.
  • a hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are preferably used as aminoalkane phosphonates.
  • Phosphonates are contained in viscoelastic, solid surfactant compositions according to the invention preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight, in each case based on the total weight of the composition.
  • the combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred (particularly for use in dishwashing detergents). These can be used in the amounts mentioned above.
  • amounts of, in each case based on the total weight of the composition, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or hydrogen carbonate), and 2.5 to 7.5% by weight of phosphonate are used in the surfactant compositions according to the invention.
  • compositions according to the invention are characterized in that they contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and optionally phosphonate.
  • this is selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA.
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the weight percent of the additional phosphorus-free builder, in particular MGDA and/or GLDA is preferably 0 to 40 weight percent, in particular 5 to 30 weight percent, above all 7 to 25 weight percent.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and/or have a lower hygroscopicity (water absorption at 25°C, normal pressure) compared to the non-granulated powder are advantageous.
  • the combination of at least three, in particular at least four builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of surfactant compositions according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • dishwashing detergents preferably automatic dishwashing detergents.
  • other builders can also be included.
  • Polymeric polycarboxylates are also suitable as organic builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 1,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 1,100 to 10,000 g/mol, and particularly preferably of 1,200 to 5,000 g/mol, can be preferred.
  • the viscoelastic, solid surfactant compositions according to the invention can further contain crystalline layered silicates of the general formula NaMSi x O 2x+1 ⁇ y as builder.
  • H 2 O where M is sodium or hydrogen
  • x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4
  • y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a Na 2 O:SiO 2 modulus of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably dissolving-retarded and have secondary washing properties, can also be used.
  • An optical brightener is preferably selected from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocycle-substituted pyrene derivatives and mixtures thereof.
  • optical brighteners include disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene disulfonate (for example available as Tinopal ® DMS from BASF SE), disodium 2,2'-bis-(phenyl-styryl)disulfonate (for example available as Tinopal ® CBS from BASF SE), 4,4'-bis[(4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disulfonic acid (for example available as Tinopal ® UNPA from BASF SE), Hexasodium 2,2'-[vinylenebis[(3-sulphonato-4,1-phenylene)imino[6-(diethylamino)-1,3,5-triazine-4,2-diyl]imino]]bis-(benzen
  • the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and/or vinylimidazole.
  • Polymers suitable as color transfer inhibitors include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof.
  • Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) are particularly preferably used as color transfer inhibitors.
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan ® HP 50 or Sokalan ® HP 53.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) used preferably have a molecular weight in the range of 5,000 to 100,000.
  • a PVP/PVI copolymer is commercially available, for example, from BASF under the name Sokalan ® HP 56.
  • Another color transfer inhibitor that is extremely preferred is polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan ® HP 66.
  • the viscoelastic, solid surfactant composition according to the invention contains incorporated solid particles (hereinafter also referred to as particles).
  • Such dispersed solid particles are to be understood as solid substances which do not dissolve in the liquefied phase of the surfactant composition according to the invention at temperatures of up to 5°C units above the sol-gel temperature of the solid surfactant composition according to the invention and are present as a separate phase.
  • these particles are suspended in the liquid phase above the sol-gel temperature and the liquid phase is then cooled below the sol-gel temperature to obtain the viscoelastic surfactant composition according to the invention.
  • the solid particles are preferably selected from polymers, pearlescent pigments, microcapsules, speckles or mixtures thereof.
  • Microcapsules in the sense of the present invention include any type of capsule known to the person skilled in the art, but in particular core-shell capsules and matrix capsules.
  • Matrix capsules are porous molded bodies that have a structure similar to a sponge.
  • Core-shell capsules are molded bodies that have a core and a shell.
  • Suitable microcapsules are those capsules that have an average diameter X 50.3 (volume average) of 0.1 to 200 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 5 to 80 ⁇ m, particularly preferably 10 to 50 ⁇ m and in particular 15 to 40 ⁇ m.
  • the average particle size diameter X 50.3 is determined by sieving or using a Camsizer particle size analyzer from Retsch.
  • microcapsules of the invention preferably contain at least one active ingredient, preferably at least one fragrance. These preferred microcapsules are perfume microcapsules.
  • the microcapsules have a semipermeable capsule wall (shell).
  • a semipermeable capsule wall in the sense of the present invention is a capsule wall that is semi-permeable, i.e. it continuously releases small amounts of the capsule core over time without the capsule being damaged or opened, for example by friction.
  • Such capsules continuously release small amounts of the active ingredient in the capsule, e.g. perfume, over a longer period of time.
  • the microcapsules have an impermeable shell.
  • An impermeable shell in the sense of the present invention is a capsule wall that is essentially impermeable, i.e. the capsule core is only exposed when the capsule is damaged or opened.
  • Such capsules contain significant amounts of the at least one fragrance, so that if the capsule is damaged or opened, a very intense scent is provided.
  • the scent intensities achieved in this way are usually so high that smaller quantities of microcapsules can be used to achieve the same scent intensity as with conventional microcapsules.
  • the surfactant composition according to the invention contains both microcapsules with a semi-permeable shell and microcapsules with an impermeable shell.
  • composition according to the invention can also contain two or more different types of microcapsules with a semipermeable or impermeable shell.
  • High molecular weight compounds are usually suitable as materials for the shell of the microcapsules, such as protein compounds such as gelatin, albumin, casein and others, cellulose derivatives such as methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose and others, and above all synthetic polymers such as polyamides, polyethylene glycols, polyurethanes, epoxy resins and others.
  • Melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer is preferably used as the wall material, i.e. as the shell.
  • Capsules according to the invention are used, for example, but not exclusively, in US 2003/0125222 A1 , EN 10 2008 051 799 A1 or WO 01/49817 described.
  • Preferred melamine-formaldehyde microcapsules are prepared by condensing melamine-formaldehyde precondensates and/or their C 1 -C 4 alkyl ethers in water in which the at least one odor modulator compound and optionally further ingredients, such as at least one fragrance, are present in the presence of a protective colloid.
  • Suitable protective colloids are, for example, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and methylcellulose, polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, gelatin, gum arabic, xanthan gum, alginates, pectins, degraded starches, casein, polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, water-soluble polymers containing sulfonic acid groups and containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, as well as polymers of N-(sulfoethyl)-maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acids and formaldehyde as well as con
  • At least one cationic polymer made of Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-9, Polyquaternium-10, Polyquaternium-11, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-19, Polyquaternium-20, Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29, Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35,
  • Preferably usable microcapsules have average diameters X 50.3 in the range from 1 to 100 ⁇ m, preferably from 5 to 95 ⁇ m, in particular from 10 to 90 ⁇ m, for example from 10 to 80 ⁇ m.
  • the shell of the microcapsules enclosing the core or (filled) cavity preferably has an average thickness in the range of about 5 to 500 nm, preferably from about 50 nm to 200 nm, in particular from about 70 nm to about 180 nm.
  • Pearlescent pigments are pigments that have a pearlescent sheen.
  • Pearlescent pigments consist of thin flakes that have a high refractive index and are partially reflecting light and partially transparent to light. The pearlescent sheen is created by interference of the light hitting the pigment (interference pigment).
  • Pearlescent pigments are usually thin flakes of the above-mentioned material, or contain the above-mentioned material as thin multilayer films or as parallel components in a suitable carrier material.
  • the pearlescent pigments that can be used according to the invention are either natural pearlescent pigments such as fish silver (guanine/hypoxanthine mixed crystals from fish scales) or mother of pearl (from ground mussel shells), monocrystalline flake-shaped pearlescent pigments such as bismuth oxychloride and pearlescent pigments based on mica and mica/metal oxide.
  • the latter pearlescent pigments are mica that has been coated with a metal oxide.
  • Pearlescent pigments based on mica and mica/metal oxide are preferred according to the invention.
  • Micas belong to the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite.
  • the mica predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include TiO 2 , Cr 2 O 3 and Fe 2 O 3 .
  • interference pigments and colored luster pigments are obtained as pearlescent pigments according to the invention. In addition to a glittering optical effect, these types of pearlescent pigment also have color effects.
  • the pearlescent pigments that can be used according to the invention can also contain a color pigment that is not derived from a metal oxide.
  • the grain size of the preferably used pearlescent pigments is preferably an average diameter X 50.3 (volume average) between 1.0 and 100 ⁇ m, particularly preferably between 10.0 and 60.0 ⁇ m.
  • speckles are understood to mean macroparticles, in particular macrocapsules, which have an average diameter X 50.3 (volume average) of more than 300 ⁇ m, in particular from 300 to 1500 ⁇ m, preferably from 400 to 1000 ⁇ m.
  • Speckles are preferably matrix capsules.
  • the matrix is preferably colored. Matrix formation occurs, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art, as is the production of particles with these matrix-forming materials.
  • An example of a matrix-forming material is alginate.
  • an aqueous alginate solution which may also contain the active ingredient(s) to be included, is dripped and then hardened in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • other matrix-forming materials can be used instead of alginate.
  • the surfactant compositions according to the invention contain in a preferred embodiment as a further component at least one zinc salt as a glass corrosion inhibitor.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water of above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20°C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is present in surfactant compositions according to the invention preferably in an amount of 0.01% to 5% by weight, particularly preferably in an amount of 0.05% to 3% by weight, in particular in an amount of 0.1% to 2% by weight, based on the total weight of the composition.
  • polyethyleneimines such as those available under the name Lupasol® (BASF)
  • BASF can be used as glass corrosion inhibitors, preferably in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight.
  • the viscoelastic solid surfactant composition of the present invention necessarily contains at least one said organic compound of component (ii).
  • surfactant compositions in which the carbocyclic structural unit b) is selected from at least one optionally substituted aryl group, in particular one optionally substituted phenyl group are preferably suitable. It is particularly preferred if a substituted aryl group, in particular a substituted phenyl group, is substituted by at least one of the following radicals: a hydroxy group, a (C 1 -C 6 )-alkyl group, a (C 2 -C 6 )-alkenyl group, a (C 2 -C 6 )-acyl group, a (C 2 -C 6 )-acyloxy group, a (C 1 -C 6 )-alkoxy group, an amino group, a (C 2 -C 6 )-acylamino group, a (C 1 -C 6 )-alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryl
  • the further cyclic structural unit c) is different from the carbocyclic structural unit b).
  • the further cyclic structural unit c) binds covalently to the carbocyclic structural unit b) either directly or via a divalent, bridging structural unit (preferably via (C 1 -C 4 )-alkanediyl).
  • the carbon atoms of the at least two carbonyl groups from the further cyclic structural unit c) form rings.
  • the further cyclic structural unit c) is selected from at least one 2,5-diketopiperazine structural unit.
  • Preferred viscoelastic, solid surfactant compositions of the invention contain, based on the total weight of the composition, organic compound of component (ii) in a total amount of at least 0.5% by weight, in particular from 0.5 to 3.0% by weight. It has again proven to be particularly preferred if the surfactant compositions according to the invention (in each case based on the total weight of the composition) contain organic compound of component (ii) in a total amount of at least 0.55% by weight, in particular of at least 0.7% by weight, particularly preferably of at least 0.8% by weight.
  • organic compound of component (ii) in a total amount of from 0.5 to 3.0 wt.%, in particular from 0.7 to 2.5 wt.%, very particularly preferably from 0.8 to 2.0 wt.%, most preferably from 0.85 to 1.5 wt.%.
  • Surfactant compositions according to the invention therefore contain as component (ii) at least one 2,5-diketopiperazine compound of the formula (I) wherein R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a hydroxy group, a (C 1 -C 6 )-alkyl group, a (C 2 -C 6 )-alkenyl group, a (C 2 -C 6 )-acyl group, a (C 2 -C 6 )-acyloxy group, a (C 1 -C 6 )-alkoxy group, an amino group, a (C 2 -C 6 )-acylamino group, a (C 1 -C 6 )-alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an
  • a radical other than a hydrogen atom is preferably understood to mean all radicals defined under the definitions of R 5 and R 1 according to formula (I) which are other than a hydrogen atom, in particular a hydroxy group, an amino group, a (C 1 -C 6 )-alkyl group, a (C 2 -C 6 )-alkenyl group, a (C 2 -C 6 )-acyl group, a (C 2 -C 6 )-acyloxy group, a (C 1 -C 6 )-alkoxy group, an amino group, a (C 2 -C 6 )-acylamino group, a (C 1 -C 6 )-alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl-(C 1 -C 4 )-alkyloxy group, an aryl-(C 1 -C 3 )-alkyl group
  • an alkyl group (or an alkyl structural fragment of a more complex group) is a group selected from linear alkyl group, branched alkyl group or cyclic alkyl group (also: cycloalkyl group).
  • Preferred linear or branched (C 1 -C 6 )-alkyl groups are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl.
  • Preferred branched (C 3 -C 10 )-alkyl groups are selected from iso-propyl, sec-butyl, iso-butyl, tert-butyl, neo-pentyl, iso-octyl, 2-ethylhexyl, 2-ethylheptyl.
  • Preferred cyclic alkyl groups ((C 3 -C 6 )-cycloalkyl groups) are selected from cyclopentyl, cyclohexyl.
  • Preferred (C 2 -C 6 )-alkenyl groups are selected from vinyl, allyl, 2-butenyl.
  • Preferred (C 2 -C 6 )-alkynyl groups are selected from ethynyl, propargyl, but-2-ynyl, hex-3-ynyl.
  • Preferred (C 2 -C 6 )-acyl groups are selected from acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, especially acetyl.
  • Preferred (C 2 -C 6 )-acyloxy groups are selected from acetyloxy, propanoyloxy, butanoyloxy, pentanoyloxy and hexanoyloxy, especially acetyloxy.
  • an alkoxy group is understood to mean an alkyl group which is attached via an oxygen atom and is selected from a linear alkyl group, a branched alkyl group or a cyclic alkyl group (also: cycloalkyl group).
  • Preferred (C 1 -C 6 )-alkoxy groups are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy.
  • Preferred (C 2 -C 6 )-acylamino groups are acetylamino, propanoylamino, butanoylamino, pentanoylamino and hexanoylamino, in particular acetylamino.
  • Preferred aryl groups are phenyl, naphthyl, anthracenyl, which may be substituted or unsubstituted.
  • Aroyl groups are arenecarbonyl groups in which a carbonyl group binds directly to the aromatic ring system.
  • Preferred aroyl groups are benzoyl, naphthoyl and anthracenoyl, which can be substituted or unsubstituted.
  • Aroyloxy groups are aroyl groups that are bonded to the carbonyl radical via an additional oxygen atom.
  • Preferred aroyloxy groups are selected from benzoyloxy, naphthoyloxy and anthracenoyloxy, which may be substituted or unsubstituted.
  • a preferred aryloxy group is the phenoxy group or the naphthoxy group, which may be substituted or unsubstituted.
  • Preferred aryl-(C 1 -C 3 )-alkyl groups are selected from benzyl, 2-phenylethyl, naphthylmethyl, 2-naphthylethyl, which may be substituted or unsubstituted.
  • Preferred heteroaryl groups are pyridyl, pyrimidinyl, imidazolyl, indolyl, furyl, thiophenyl, 1,3,5-triazolyl
  • Preferred heteroaryl-(C 1 -C 3 )-alkyl groups are selected from furfuryl, 2-indol-3-ylethyl, indol-3-ylmethyl, pyridylmethyl, which may be substituted or unsubstituted.
  • the viscoelastic, solid surfactant compositions according to the invention contain at least one 2,5-diketopiperazine compound of the formula (I) in which R 5 represents a (C 1 -C 4 ) hydrocarbon group substituted by an aromatic radical, in particular a radical of the following formulae (IV) or (VI) ( vide infra ) .
  • Preferred viscoelastic, solid surfactant compositions of the invention contain, based on the total weight of the composition, 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.5% by weight, in particular from 0.5 to 3.0% by weight. It has again proven to be particularly preferred if the compositions according to the invention (in each case based on the total weight of the composition) contain 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.55% by weight, in particular of at least 0.7% by weight, particularly preferably of at least 0.8% by weight.
  • 2,5-diketopiperazine compound according to formula (I) is contained in a total amount of from 0.5 to 3.0 wt.%, in particular from 0.7 to 2.5 wt.%, very particularly preferably from 0.8 to 2.0 wt.%, most preferably from 0.85 to 1.5 wt.%.
  • compositions according to the invention contain at least one 2,5-diketopiperazine compound according to formula (Ia) wherein R 1 and R 5 are as defined under formula (I) (vide supra).
  • Particularly preferred compounds of formula (Ib) have the following radicals: R1 R5 Hydrogen atom 2-Carboxyethyl Hydrogen atom p-Hydroxybenzyl Hydroxy group p-Hydroxybenzyl Hydrogen atom 2-(Benzyloxycarbonyl)ethyl Hydrogen atom 4-Imidazolylmethyl Hydrogen atom methyl Benzyloxy p-(benzyloxy)-benzyl
  • radicals R 1 to R 5 apply to compounds of the formula (I), but also to compounds of the formulas (Ia) and (Ib), with the proviso that for the formulas (Ia) and (Ib) the radicals R 2 , R 3 and R 4 necessarily represent a hydrogen atom.
  • composition according to the invention contains at least one compound of the formula (I) in which, according to formula (I), the radicals R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a benzyl group, a methoxy group, a (C 2 -C 6 )-acyloxy group, an aryloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.
  • the radicals R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group, a methyl group, an eth
  • R' according to formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group.
  • R' according to formula (III) represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a benzyl group, a benzoyloxy group or a phenyl group.
  • R' according to formula (IV) represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a benzyl group, a benzoyloxy group or a phenyl group.
  • R" and R′′′ according to formula (V) independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a benzyl group, a benzoyl group, acetyl group, an aminoiminomethyl group or a tosyl group.
  • R according to formula (VI) represents a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a phenyl group, a methoxy group, an acetyloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.
  • radical R 1 When selecting the above-mentioned preferred radicals R 1 to R 5 , it is again preferred if, according to formula (I) and according to formulas (Ia) and (Ib), the radical R 1 binds in the para position of the phenyl ring.
  • the 2,5-diketopiperazine compounds of the formula (I) have chiral centers at least at the carbon atoms of positions 3 and 6 of the 2,5-diketopiperazine ring.
  • the numbering of ring positions 3 and 6 was illustrated by way of example in formula (I-b).
  • the 2,5-diketopiperazine compound of the formula (I) of the compositions according to the invention is preferably, based on the stereochemistry of the carbon atoms at positions 3 and 6 of the 2,5-diketopiperazine ring, the configuration isomer 3S,6S , 3R,6S , 3S,6R , 3R,6R or mixtures thereof, particularly preferably 3S,6S.
  • compositions according to the invention contain at least one 2,5-diketopiperazine compound of the formula (I) selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine (also: 3-(5-benzyl-3,6-dioxopiperazin-2-yl)propanoic acid), 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazine, 3-benzyl-6-iso-propyl-2,5-diketopiperazine, 3-benzyl-6-(4-aminobutyl)-2,5-diketopiperazine, 3,6-di(benzyl)-2,5-diketopiperazine, 3,6-di(4-hydroxybenzyl)-2,5-diketopiperazine, 3,6-Di(4-(benzyloxy)benzyl)-2,5-diketopiperazine,
  • the viscoelastic, solid surfactant compositions according to the invention preferably contain at least one 2,5-diketopiperazine compound of the formula (I) selected from 3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione, 3-benzyl-6-isopropylpiperazine-2,5-dione, 3,6-bis(4-(benzyloxy)benzyl)piperazine-2,5-dione, 3-benzyl-piperazine-2,5-dione, 3-benzyl-6-carboxymethylpiperazine-2,5-dione or mixtures thereof.
  • compounds with the aforementioned configuration isomers are preferably suitable for selection, with the S,S configuration being particularly preferred in each case.
  • (3S,6S)-3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione, (3R,6R)-3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione, (3S,6R)-3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione, (3R,6S)-3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione or mixtures thereof are contained in the surfactant compositions according to the invention as component (ii).
  • (3S,6S)-3,6-bis(4-hydroxybenzyl)piperazine-2,5-dione is again most preferred.
  • the 2,5-diketopiperazine compounds contained in the agents according to the invention are prepared by means of known synthesis methods (cf. Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237 ).
  • the viscoelastic, solid surfactant composition according to the invention contains water. It is preferred if water is contained in the surfactant composition, based on the total weight of the composition, preferably in a total amount of between 0 and 70% by weight, more preferably between 4 and 70% by weight, more preferably between 10 and 70% by weight, more preferably between 0 and 60% by weight, more preferably between 4 and 60% by weight, more preferably between 10 and 60% by weight, more preferably between 0 and 40% by weight, more preferably between 4 and 40% by weight, more preferably between 10 and 40% by weight, particularly preferably between 0 and 25% by weight, more preferably between 4 and 25% by weight, more preferably between 10 and 25% by weight.
  • the proportion of water in the surfactant composition is very particularly preferably 20% by weight or less, more preferably 15% by weight or less, more preferably 12% by weight or less, in particular between 4 and 20% by weight.
  • the data in % by weight refer to the total weight of the composition.
  • the solubility of said surfactant composition as well as its stability is improved if the surfactant composition preferably additionally contains at least one organic solvent having at least one hydroxyl group, without an amino group and having a molecular weight of at most 500 g/mol.
  • This said organic solvent is in turn preferably selected from (C 2 -C 8 )-alkanols having at least one hydroxyl group (particularly preferably selected from the group consisting of ethanol, ethylene glycol, 1,2-propanediol, glycerin, 1,3-propanediol, n-propanol, isopropanol, 1,1,1-trimethylolpropane, 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, or mixtures thereof), triethylene glycol, butyl diglycol, polyethylene glycols having a weight-average molar mass M w of at most 500 g/mol, glycerin carbonate, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2-Dimethyl
  • organic solvent is contained in a total amount of 5 to 40 wt.%, in particular 10 to 35 wt.%.
  • the surfactant composition preferably additionally containing at least one polyalkylene oxide compound having a weight-average molar mass M w of at least 4000 g/mol, in particular of at least 6000 g/mol, more preferably of at least 8000 g/mol.
  • polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof.
  • polyethylene oxide having a weight-average molar mass M w of at least 4000 g/mol, in particular of at least 6000 g/mol, more preferably of at least 8000 g/mol, is used as the polyalkylene oxide compound.
  • the stability of said surfactant composition is further improved if the surfactant composition additionally contains at least one polymeric polyol, in particular polyvinyl alcohol.
  • polymeric polyols have more than 3 hydroxyl groups. Suitable polymeric polyols preferably have an average molecular weight of 4000 to 100,000 g/mol.
  • the surfactant composition according to the invention preferably contains, based on its total weight, a total amount of 1 to 30% by weight, in particular 2 to 20% by weight, of the polymeric polyol.
  • Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by hydrolysis of polyvinyl acetate.
  • Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents.
  • Polyvinyl alcohols with an average molecular weight of 30,000 to 60,000 g/mol are preferred.
  • Preferred polyvinyl alcohols are those which are in the form of white-yellowish powders or granules with degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g/mol) and degrees of hydrolysis of 87-99 mol%, which accordingly still contain a residual content of acetyl groups.
  • the surfactant composition comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and above all 82 to 88 mol%.
  • the water-soluble packaging consists of at least 20 wt.%, particularly preferably at least 40 wt.%, very particularly preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • PVOH powders with the above-mentioned properties which are suitable for use in the at least one second phase, are sold, for example, under the name Mowiol ® or Poval ® by Kuraray.
  • the Poval ® grades are particularly suitable, in particular grades 3-83, 3-88 and 3-98, as well as Mowiol ® 4-88 from Kuraray.
  • the water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good cold water solubility.
  • the reaction products of polyvinyl alcohol and starch are extremely advantageous to use.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • PVOH and/or gelatin are particularly suitable for producing surfactant compositions which satisfy the requirements shown above.
  • a surfactant composition according to the invention which comprises PVOH and at least one organic solvent as described above is therefore particularly preferred.
  • the composition additionally contains at least one stabilizer selected from magnesium oxide, inorganic salt of Mg, Ca, Zn, Na or K (in particular sulfate, carbonate or acetate, more preferably magnesium sulfate, zinc acetate or calcium acetate), acetamide monoethanolamine, hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof.
  • at least one stabilizer selected from magnesium oxide, inorganic salt of Mg, Ca, Zn, Na or K (in particular sulfate, carbonate or acetate, more preferably magnesium sulfate, zinc acetate or calcium acetate), acetamide monoethanolamine, hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof.
  • the viscoelastic, solid surfactant composition contains at least one bittering agent to increase product safety.
  • Preferred bittering agents have a bitterness value of at least 1,000, preferably at least 10,000, particularly preferably at least 200,000.
  • the standardized procedure described in the European Pharmacopoeia 5th edition, basic work, Stuttgart 2005, Volume 1, General Part, Monograph Groups, 2.8.15, Bitterness Value, p. 278) is used.
  • bittering agents are selected from denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof, particularly preferably denatonium benzoate.
  • Glycosides are organic compounds of the general structure R-O-Z, in which an alcohol (R-OH) is linked to a sugar moiety (Z) via a glycosidic bond.
  • Suitable glycosides are, for example, flavonoids such as quercetin or naringin or iri doidglycosides such as aucubin and in particular secoiri doidqlvcosides such as amarogentin, dihydrofoliamentin, gentiopicroside, gentiopikrin, swertiamarin, sweroside, gentioflavoside, centauroside, methiafolin, harpagoside and centapikrin, sailicin or condurangin.
  • Isoprenoids are compounds that are formally derived from isoprene. Examples include terpenes and terpenoids.
  • Suitable isoprenoids include, for example, sequiterpene lactones such as absinthin, artabsin, cnicin, lactucin, lactucine or salonitenolide, monoterpene ketones (thujones) such as ⁇ -thujone or ⁇ -thujone, tetranortriterpenes (limonoids) such as deoxylimonene, deoxylimonene acid, limonin, ichangin, iso-obacunonic acid, obacunone, obacunonic acid, nomilin or nomilic acid, terpenes such as marrubin, premarrubin, carnosol, carnosolic acid or quassin.
  • sequiterpene lactones such as absinthin, artabsin, cnicin, lactucin, lactucine or salonitenolide
  • monoterpene ketones such as ⁇ -thujone or ⁇ -thujone
  • Alkaloids are naturally occurring, chemically heterogeneous, mostly alkaline, nitrogen-containing organic compounds of secondary metabolism that act on the animal or human organism.
  • Suitable alkaloids include quinine hydrochloride, quinine hydrogen sulfate, quinine dihydrochloride, quinine sulfate, columbine and caffeine.
  • Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.
  • the viscoelastic, solid surfactant composition preferably contains bittering agents in a total amount of at most 1 part by weight of bittering agent to 250 parts by weight of viscoelastic, solid surfactant composition (1:250), particularly preferably at most 1:500, very particularly preferably at most 1:1000, based on its total weight.
  • the viscoelastic, solid surfactant composition can be prepared by first bringing a liquid composition containing organic compound of component (ii) to a temperature above the sol-gel transition temperature of the liquid composition, and then placing the heated liquid composition in a mold, preferably in a cavity of a trough mold, and cooling it in said mold to below the sol-gel transition temperature to form a viscoelastic, solid molded body.
  • the respective liquid composition is brought in the mold to below the sol-gel transition temperature of the liquid composition in order to harden the liquid composition.
  • the liquid composition is cooled to not less than 20°C, in particular not less than 25°C, particularly preferably not less than 30°C, to form the said molded body.
  • the sol-gel temperature can be determined using conventional methods.
  • the organic compound of component (ii) was homogenized in water at 133°C in a closed vessel with pressure equalization in the heating thermoshaker at 400 rpm until the organic compound of component (ii) had completely dissolved and a transparent solution was formed. This solution was cooled in the heating thermoshaker to 80°C at 0 rpm.
  • a temperature-dependent oscillating measurement (devices as before ( vide supra )) was carried out at a deformation of 0.1%, a frequency of 1 Hz and a cooling rate of 5°C/min.
  • the temperature is set to 80°C and the upper plate is lowered to minimize the temperature difference between the lower and upper measuring plate.
  • the upper measuring plate is raised and 0.5 g of the sample is carefully applied as a sol to the lower plate using a pipette. The upper plate is then lowered and the measurement started. The measurements are carried out at different temperatures.
  • a corresponding molded body can also be produced by extrusion of the viscoelastic, solid surfactant composition, with subsequent rounding if necessary. This can produce a free-flowing product or pellets.
  • the viscoelastic, solid surfactant composition of the first subject matter of the invention is present as a shaped body.
  • a molded body is a single body that stabilizes itself in its imprinted shape.
  • This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately shaping this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then hardening the liquid composition, e.g. in a sol-gel process.
  • All imaginable shapes are possible, such as a sphere, cube, cuboid, round disk, tub, bowl, prism, octahedron, tetrahedron, egg shape, dog, cat, mouse, horse, torso, bust, pillow, automobile, oval disk with an embossed trademark, and much more.
  • the shaped body of the viscoelastic, solid surfactant composition of the first subject matter of the invention has a weight of at least 1 g, preferably of at least 5 g, particularly preferably of at least 10 g.
  • the molded body according to the invention of the viscoelastic, solid surfactant composition of the first subject matter of the invention has a weight of at most 80 g, in particular of at most 70 g, particularly preferably of at most 50 g, very particularly preferably of at most 40 g, most preferably of at most 30 g.
  • the aforementioned minimum weights of the molded body are particularly preferred.
  • the shaped body of the viscoelastic, solid surfactant composition of the first subject matter of the invention most preferably has a weight of 10 to 80 g, in particular 10 to 70 g, more preferably 10 to 50 g, most preferably 10 to 30 g, for example 15 g or 25 g. It is again preferred if the said shaped body contains surfactant in the total amounts identified as preferred (vide supra).
  • the molded body of said viscoelastic, solid composition may also contain at least two different viscoelastic, solid surfactant compositions of the first Subject matter of the invention with the formation of at least two phases, preferably at least two differently colored phases.
  • a trough-shaped body can be produced as the first phase from a first viscoelastic, solid surfactant composition of the first subject matter of the invention, into the trough of which a second viscoelastic, solid surfactant composition of the first subject matter of the invention is introduced as the second phase.
  • the shaped body can also be formed from various viscoelastic, solid compositions which are arranged as layered phases.
  • a corresponding trough-shaped body of the surfactant composition according to the invention can preferably be designed as a container with at least one trough, e.g. in the form of a tub or bowl, such that the volume of the walls is smaller than the total volume of all the troughs.
  • the walls of a trough-shaped body of this embodiment preferably have an average thickness of a maximum of 5 mm, in particular a maximum of 2 mm, more preferably a maximum of 1 mm.
  • the total volume of the troughs of this embodiment preferably has a volume of at least 5 ml, in particular at least 10 ml, more preferably at least 15 ml.
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • One phase differs from another phase by various features, for example ingredients, external appearance, etc.
  • different phases can be visually distinguished.
  • a first phase can be clearly distinguished from a second phase.
  • these can preferably also be distinguished from one another with the naked eye because they differ from one another, for example in terms of color.
  • a visual distinction between the phases for example due to a difference in color or transparency, is preferably possible.
  • Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye.
  • the individual phases can have different properties when used.
  • At least one bittering agent is incorporated homogeneously into the molded body and/or the surface of the molded body is coated with at least one bittering agent. It is preferred to incorporate the at least one bittering agent homogeneously into the molded body as an ingredient of the viscoelastic, solid surfactant composition.
  • Preferred bittering agents and amounts are those mentioned above (vide supra).
  • powdering agents are selected from talcum, sodium sulfate, starch, pectin, amylopectin, dextrin, lactic acid, lactose or mixtures thereof.
  • the surfaces of the molded body can be printed for further aesthetic enhancement and/or to add information or manufacturer names.
  • the use of inkjet printing is preferred.
  • a second subject matter of the invention is a portion containing at least one viscoelastic, solid surfactant composition of the first subject matter of the invention.
  • the portion contains the viscoelastic, solid surfactant composition of the first subject matter of the invention as a shaped body. It is in turn preferred if the portion contains the shaped body to an extent of at least 5% by weight, in particular at least 15% by weight, in particular at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, particularly preferably at least 95% by weight, based on its total weight.
  • a portion is an independent dosing unit that provides a quantity of textile treatment agent for one application, preferably for use in a washing machine.
  • the viscoelastic, solid surfactant composition according to the invention can either be the only textile treatment agent in the portion, or can be formulated in the portion together with at least one additional composition that is different from the viscoelastic, solid surfactant composition of the first subject matter of the invention and together form the textile treatment agent of the portion.
  • the portion according to the invention contains at least one shaped body of the viscoelastic, solid surfactant composition of the first subject matter of the invention, which has a weight of at least 1 g, preferably of at least 5 g, particularly preferably of at least 10 g.
  • the portion according to the invention contains at least one shaped body of the viscoelastic, solid surfactant composition of the first subject matter of the invention, which has a weight of at most 80 g, in particular of at most 70 g, particularly preferably of at most 50 g, very particularly preferably of at most 40 g.
  • the above-mentioned minimum weights of the molded body are particularly preferred.
  • the portion according to the invention comprises a shaped body of the viscoelastic, solid surfactant composition of the first subject matter of the invention with a weight of 1 to 80 g, in particular 1 to 70 g, more preferably 1 to 50 g, further preferably 1 to 30 g, in particular 10 to 80 g, in particular 10 to 70 g, more preferably 10 to 50 g, most preferably 10 to 30 g, for example 15 g or 25 g. It is again preferred if the said shaped body contains surfactant in the total amounts identified as preferred (vide supra).
  • the molded body is preferably coated with water-soluble material.
  • Such a coating has also proven to be advantageous with regard to the storage stability of the molded bodies according to the invention used in the portions.
  • the said molded body of the portion is coated on the surface with at least one water-soluble material, preferably with at least one water-soluble polymer.
  • the coating can be carried out, for example, by spraying on a solution or by immersing in a melt, with the melting temperature in the latter method preferably being below the sol-gel temperature. It may in turn be preferred to powder the molded bodies coated with at least one water-soluble material with at least one powdered solid. Preferred means for powdering are those mentioned above (vide supra).
  • a portion according to the invention can contain at least one chamber with walls made of water-soluble material, into which at least one molded body of a viscoelastic, solid surfactant composition of the first subject matter of the invention is introduced. Added together across all the chambers of the portion, the total compositions made up therein result in the product to be dosed in the portion (here a textile treatment agent).
  • a textile treatment agent a viscoelastic, solid surfactant composition of the first subject matter of the invention
  • a chamber is a space delimited by walls (e.g. a film) which can also exist without the product to be dosed (possibly by changing its shape).
  • a layer of a surface coating therefore explicitly does not fall under the definition of a wall.
  • the water-soluble material forms the walls of the chamber and thus envelops the composition of the textile treatment agent.
  • a material is water-soluble if, at 20°C, 0.1 g of the material dissolves in 800 mL of water within 600 seconds while stirring (magnetic stirrer speed 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm, 1000 mL low-form beaker from Schott, Mainz) to such an extent that no individual solid particles of the material are visible to the naked eye.
  • the water solubility of the material in the form of a film used for the production of pouches for wrapping can be determined using a square film of the material in question (film: 22 ⁇ 22 mm with a thickness of 76 ⁇ m) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol.
  • the framed film in question is immersed in 800 mL of distilled water tempered to 20 °C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, beaker 1000 mL, low form) so that the surface of the clamped film is arranged at a right angle to the bottom surface of the beaker, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame is aligned parallel to the bottom surface of the beaker in such a way that the lower edge of the frame runs along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is positioned above the center of the radius of the beaker bottom.
  • the material should dissolve within 600 seconds when stirred (magnetic stirrer speed 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) to such an extent that no individual solid film particles are visible to the naked eye.
  • the water-soluble material generally used to envelop the molded body preferably contains at least one water-soluble polymer. It is particularly preferred that the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble material and water-soluble films as water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if the water-soluble material comprises at least one polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • 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 additionally be added to the water-soluble material.
  • preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the water-soluble material of the film material used to provide the pouch walls has a preferred thickness in a range from 65 to 180 ⁇ m, in particular from 70 to 150 ⁇ m, more preferably 75 to 120 ⁇ m.
  • a bittering agent is preferably incorporated into the water-soluble material of the coating of the molded body of the portion or the walls of the pouch of the portion.
  • Corresponding embodiments of the water-soluble material with bittering agent are described in the publications EP-B1-2 885 220 and EP-B1-2 885 221
  • a preferred bittering agent is selected from the aforementioned bittering agents (vide supra), in particular denatonium benzoate.
  • Portions according to the invention in the form of a pouch can be produced either by vertical form-fill-seal (VFFS) or thermoforming processes.
  • Walls of at least one chamber are particularly preferably produced by sealing at least one film of water-soluble material, in particular by sealing in a form-fill-seal process.
  • the thermoforming process generally includes forming a first layer of a water-soluble film material to form at least one recess for receiving at least one composition therein, filling the composition into the respective recess, covering the recesses filled with the composition with a second layer of a water-soluble film material and sealing the first and second layers to one another at least around the recesses.
  • Thin layer chromatography was carried out on silica gel 60 plates coated with a fluorescent marker ( Macherey-Nagel, ALUGRAM Xtra SIL G/UV254) and visualized using UV light (254 nm/366 nm). If necessary, ninhydrin was also used. Column chromatography was carried out with silica gel (0.040 - 0.063 mm).
  • IR spectra were measured on a Nicolet Thermo iS10 scientific spectrometer with diamond ATR unit. The absorption bands were expressed in cm -1 with the following relative intensity: s (strong, 0 - 33 % T); m (medium, 34 - 66 % T), w (weak, 67 - 100 % T), and br (broad).
  • the dipeptide (1.0 eq) was dissolved in CH 2 Cl 2 (0.4 M) and cooled to 0 °C.
  • TFA (5.0 eq) was added in one portion and stirred until the starting material was converted. During this time, the reaction mixture was slowly warmed to 25 °C. All volatile components were removed under reduced pressure and the residue was coevaporated with toluene (5 ⁇ ) to remove residual TFA.
  • the TFA salt was isolated as a colorless solid.
  • the TFA salt (1.0 eq) was dissolved in 2-butanol (0.1 M) and AcOH (3.0 eq) and NEts (2.0 eq) were added. The mixture was stirred at 80 °C until complete conversion of the starting material and finally cooled to 25 °C. The precipitate was filtered off, washed with THF (3 ⁇ ) and dried under fine vacuum. Finally, the cyclized dipeptide was obtained as a colorless solid.
  • the cyclized dipeptide still contained protective groups, these were removed by hydrogenation.
  • the protected cyclic dipeptide was mixed in MeOH (0.1 M) and palladium on activated carbon (5 mol%) was added. The suspension was saturated with hydrogen and stirred at 25 °C until complete conversion. After filtration and removal of the solvent under reduced pressure, the deprotected cyclic dipeptide was isolated as a colorless solid.
  • IR (ATR, pure): ⁇ 3516 (w), 3145 (w), 1665 (s), 1614 (m), 1598 (m), 1515 (s), 1456 (s), 1378 (w), 1337 (m), 1308 (f), 1272 (m), 1237 (s), 1173 (m), 1104 (m), 1085 (f), 1013 (f), 950 (f), 925 (f), 884 (w), 825 (s), 796 (s), 776 (s), 717 (m) cm -1 .
  • compositions E1 to E5 were prepared (cf. Table 2.2 in conjunction with Table 2.1).
  • a premix was first prepared as a solution of 1.0 g (3S, 6S)-3,6-di(4-hydroxybenzyl)-2,5-diketopiperazine (DKP 10) and 92 g of the selected liquid detergent in Table 3.1 while heating. 15 g of the still hot and clear premix were incorporated into 85 g of the liquid detergent in Table 3.1 at room temperature while stirring vigorously. 19 g of the resulting solution were quickly poured into a cube mold. The temperature of the solution in the mold was gradually reduced to room temperature. After solidification, the molded article was removed from the mold.
  • liquid dishwashing detergents G1 and G2 were prepared according to Table 4.1.
  • Table 4.1 Liquid dishwashing detergents G1 & G2 for the machine G1 [Wt.%] G2 (Phase 1) [Wt.%] G2 (Phase 2) [Wt.%] Glycerine 2.50 - - CaCl2 - 0.27 - Sorbitol - 8.40 - Boric acid - 3.00 - Xanthan 0.50 - - Sulfopolymer 7.5 5.70 - GLDA, tetrasodium salt 18,00 9.40 14.10 HEDP - - 2.58 citric acid 5.00 3.00 11.40 Phosphonate 0.6 - - Non-ionic surfactant 3.00 3.50 - Monoethanolamine 4.00 - 2.75 KOH (50%) - 2.43 2.35 soda - - 9.00 Cationic rinse aid polymer 0.2 - - Amylase (wt% active enzyme) 0.0125
  • a premix was first prepared from the liquid dishwashing detergent G1 from Table 4.1 as a solution of 1.0 g (3S, 6S)-3,6-di(4-hydroxybenzyl)-2,5-diketopiperazine (DKP 10) and 92 g G1 from Table 4.1 by heating. 15 g of the still hot and clear premix were incorporated into 85 g of the dishwashing detergent G1 from Table 4.1 at room temperature with vigorous stirring. 19 g of the resulting solution were quickly poured into a cube mold. The temperature of the solution in the mold was gradually reduced to room temperature. After solidification, the molded body was removed from the mold.
  • DKP 10 liquid dishwashing detergent
  • a first premix was prepared from the liquid dishwashing detergent G2 (phase 1) from Table 4.1 as a solution of 1.0 g (3S, 6S)-3,6-di(4-hydroxybenzyl)-2,5-diketopiperazine (DKP 10) and 92 g G2 (phase 1) from Table 4.1 while heating.
  • a second premix was prepared analogously from the composition G2 (phase 2) from Table 4.1.
  • phase 1 After solidification, the molded body of phase 1 was left in the cavity. 15 g of the still hot and clear premix 2 were incorporated into 85 g of the room-temperature dishwashing detergent G2 (phase 2) from Table 4.1 with vigorous stirring. 9.5 g of the resulting solution were quickly poured into the cube cavity mold on top of the already hardened molded body of G2 (phase 1). The temperature of the solution in the cavity was gradually reduced to room temperature.
  • the resulting molded body made of G2 was removed from the mold after curing of phase 2.
  • a stable, one-piece molded body with two phases (red and blue) was obtained.

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Claims (14)

  1. Composition tensioactive solide viscoélastique, contenant, par rapport à son poids total,
    (i) une quantité totale allant de 0,1 à 70 % en poids d'au moins un tensioactif et
    (ii) au moins un composé organique comportant une masse moléculaire < 1000 g/mol, une solubilité dans l'eau inférieure à 0,1 g/L (20 °C, pH 7) et une structure contenant
    a) au moins deux groupes choisis parmi -OH, -NH-, ou des mélanges de ceux-ci, et
    b) au moins un motif constitutif carbocyclique comportant au moins deux liaisons doubles endocycliques, en particulier au moins un motif constitutif aromatique carbocyclique, et
    c) au moins un autre motif constitutif cyclique qui présente au moins deux groupes carbonyle
    et
    (iii) de l'eau,
    dans laquelle le composant (ii) est choisi parmi au moins un composé de dicétopipérazine de formule (I)
    Figure imgb0039
    où
    R1, R2, R3 et R4 représentent indépendamment les uns des autres un atome d'hydrogène, un groupe hydroxy, un groupe alkyle en (C1-C6), un groupe alcényle en (C2-C6), un groupe acyle en (C2-C6), un groupe acyloxy en (C2-C6), un groupe alcoxy en (C1-C6), un groupe amino, un groupe acylamino en (C2-C6), un groupe alkylaminocarbonyle en (C1-C6), un groupe aryle, un groupe aroyle, un groupe aroyloxy, un groupe aryloxy, un groupe aryl-alkyloxy en (C1-C4), un groupe aryl-alkyle en (C1-C3), un groupe hétéroaryle, un groupe hétéroaryl-alkyle en (C1-C3), un groupe hydroxyalkyle en (C1-C4), un groupe aminoalkyle en (C1-C4), un groupe carboxy-alkyle en (C1-C3), dans laquelle au moins deux des radicaux R1 à R4 peuvent former conjointement avec la molécule résiduelle un cycle à 5 ou 6 chaînons,
    R5 représente un atome d'hydrogène, un groupe alkyle en (C1 à C6) linéaire, un groupe alkyle en (C3 à C10) ramifié, un groupe cycloalkyle en (C3 à C6), un groupe alcényle en (C2-C6), un groupe alcinyle en (C2-C6), un groupe hydroxyalkyle en (C1-C4), un groupe alcoxy en (C1- C4)-alkyle en (C1-C4), un groupe acyloxy en (C1-C4)-alkyle en (C1-C4), un groupe aryloxy-alkyle en (C1-C4), un groupe O-(aryl-alkyl en (C1-C4))oxy-alkyle en (C1-C4), un groupe alkylsulfanyl en (C1-C4)-alkyle en (C1-C4), un groupe aryle, un groupe aryl-alkyle en (C1-C3), un groupe hétéroaryle, un groupe hétéroaryl-alkyle en (C1-C3), un groupe hydroxyalkyle en (C1-C4), un groupe aminoalkyle en (C1-C4), un groupe N-alkylamino en (C1-C4)-alkyle en (C1-C4), un groupe N,N-dialkylamino en (C1-C4)-alkyle en (C1-C4), un groupe N-acylamino en (C2-C8)-alkyle en (C1-C4), un groupe N-acyl en (C2-C8)-N-alkylamino en (C1-C4)-alkyle en (C1-C4), un groupe N-aroyl en (C2-C8)-N-alkylamino en (C1-C4)-alkyle en (C1-C4), un groupe N,N-diacylamino en (C2-C8)-alkyle en (C1-C4), un groupe N-(aryl-alkyl en (C1-C4))amino-alkyle en (C1-C4), un groupe N,N-di(aryl-alkyl en (C1-C4))amino-alkyle en (C1-C4), un groupe carboxyalkyle en (C1-C4), un groupe alkoxycarbonyl en (C1-C4)-alkyle en (C1-C3), un groupe acyloxy en (C1-C4)-alkyle en (C1-C3), un groupe guanidinoalkyle en (C1-C3), un groupe aminocarbonyl-alkyle en (C1-C4), un groupe N-alkylaminocarbonyl en (C1-C4)-alkyle en (C1-C4), un groupe N,N-di(alkyl en (C1-C4))aminocarbonyl-alkyle en (C1-C4), un groupe N-acylaminocarbonyl en (C2-C8)-alkyle en (C1-C4), un groupe N,N-diacylaminocarbonyl en (C2-C8)-alkyle en (C1-C4), un groupe N-acyl en (C2-C8)-N-alkylaminocarbonyl en (C1-C4)-alkyle en (C1-C4), un groupe N-(aryl-alkyl en (C1-C4))aminocarbonyl-alkyle en (C1-C4), un groupe N-(aryl-alkyl en (C1-C4))-N-alkylaminocarbonyl en (C1-C6)-alkyle en (C1-C4) ou un groupe N,N-di(aryl-alkyl en (C1-C4))aminocarbonyl-alkyle en (C1-C4).
  2. Composition selon la revendication 1, caractérisée en ce que la composition tensioactive présente un module de stockage compris entre 103 Pa et 108 Pa, de préférence entre 104 Pa et 108 Pa, et un module de perte (à 20 °C, une déformation de 0,1 % et une fréquence de 1 Hz), et le module de stockage est au moins deux fois plus grand que le module de perte dans la plage de fréquences comprise entre 10-3 Hz et 102 Hz, de préférence au moins cinq fois plus grand que le module de perte, de manière particulièrement préférée au moins dix fois plus grand que le module de perte.
  3. Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle contient au moins un tensioactif anionique, de préférence au moins un tensioactif anionique choisi dans le groupe constitué d'alkylbenzènesulfonates en C8-18, oléfinesulfonates, alcanesulfonates en C12-18, estersulfonates, alkylsulfates, alcénylsulfates, éthersulfates d'alcools gras et leurs mélanges.
  4. Composition selon les revendications 1 à 3, caractérisée en ce qu'au moins un composé de formule (T-1) est contenu en tant que tensioactif,
    Figure imgb0040
     dans laquelle
    R' et R" représentent indépendamment H ou un alkyle et contiennent ensemble de 9 à 19, préférentiellement de 9 à 15 et en particulier de 9 à 13 atomes de carbone, et Y+ représente un cation monovalent ou la n-ième partie d'un cation de valence n (en particulier Na+).
  5. Composition selon l'une des revendications 1 à 4, caractérisée en ce qu'elle contient au moins un tensioactif non ionique.
  6. Composition selon l'une des revendications 1 à 5, caractérisée en ce qu'elle contient, en tant que tensioactif, au moins un tensioactif non ionique de formule (T-2)

            R2-O-(XO)m-H,     (T-2)

    dans laquelle
    R2 représente un radical alkyle en C8-C18 linéaire ou ramifié, un radical aryle ou un radical alkylaryle, XO représente indépendamment les uns des autres un groupement oxyde d'éthylène (EO) ou oxyde de propylène (PO),
    m représente des nombres entiers allant de 1 à 50.
  7. Composition selon l'une des revendications 1 à 6, caractérisée en ce que l'autre motif constitutif cyclique c) est choisi parmi au moins un motif constitutif de 2,5-dicétopipérazine.
  8. Composition selon la revendication 1, caractérisée en ce que, selon la formule (I), R1 se lie en position para du cycle phényle et de préférence R2 à R4 représentent l'hydrogène.
  9. Composition selon l'une des revendications 1 ou 8, caractérisée en ce que, selon la formule (I), R5 représente un atome d'hydrogène, un groupe méthyle, un groupe isopropyle, un groupe iso-butyle, un groupe tert-butyle, un groupe 2-(méthylsulfanyl)éthyle, un groupe hydroxyméthyle, un groupe alcoxyméthyle en (C1-C3), un groupe benzyloxyméthyle, un groupe acétyloxyméthyle, un groupe benzoyloxyméthyle, un groupe tosyloxyméthyle, un groupe 1-hydroxyéthyle, un groupe 1-(alcoxy en (C1-C3))éthyle, un groupe 1-(acétyloxy)éthyle, un groupe 1-(benzoyloxy)éthyle, un groupe 1-(tosyloxy)éthyle, un groupe mercaptométhyle, un groupe alkylsulfanylméthyle en (C1-C3), un groupe acétylsulfanylméthyle, un groupe benzoylsulfanylméthyle, un groupe tosylsulfanylméthyle, un groupe selon la formule (II),
    Figure imgb0041
    dans laquelle R' représente un atome d'hydrogène, un groupe alkyle en (C1 à C4), un groupe alcényle en (C2 à C4), un groupe aryle ou un groupe aryl-alkyle en (C1 à C4),
    un groupe selon la formule (III),
    Figure imgb0042
    dans laquelle R' représente un atome d'hydrogène, un groupe alkyle en (C1 à C4), un groupe alcényle en (C2 à C4), un groupe aryle ou un groupe aryl-alkyle en (C1 à C4),
    un groupe selon la formule (IV),
    Figure imgb0043
    dans laquelle n représente 0 ou 1, X représente un atome d'oxygène ou un groupe -NH- et R" représente un atome d'hydrogène, un groupe alkyle en (C1-C4), un groupe alcényle en (C2 à C4), un groupe aryle ou un groupe aryl-alkyle en (C1 à C4),
    un groupe selon la formule (V),
    Figure imgb0044
    dans laquelle n représente 1 ou 2 et R" et R‴ représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en (C1-C4), un groupe acyle en (C2-C6), un groupe benzoyle, un groupe aryl-alkyle en (C1 à C4), un groupe aminoiminométhyle ou un groupe tosyle,
    un groupe selon la formule (VI),
    Figure imgb0045
    dans laquelle n représente 0 ou 1 et R représente un atome d'hydrogène, un groupe hydroxy, un groupe alkyle en (C1-C4), un groupe alcoxy en (C1-C4), un groupe N-alkylamino en (C1-C4), un groupe aryl-alkyle en (C1 à C4), un groupe acétyloxy, un groupe benzoyloxy, un groupe triflyloxy ou un groupe tosyloxy.
  10. Composition selon l'une des revendications 1 à 9, caractérisée en ce que, par rapport au poids total de la composition, le composé organique du composant (ii) est contenu en une quantité d'au moins 0,5 % en poids, en particulier allant de 0,5 à 3,0 % en poids.
  11. Composition selon l'une des revendications 1 à 10, caractérisée en ce que le composé organique du composant (ii) est choisi parmi 3-benzyl-6-carboxyéthyl-2,5-dicétopipérazine, 3-benzyl-6-carboxyméthyl-2,5-dicétopipérazine, 3-benzyl-6-(4-hydroxybenzyl)-2,5-dicétopipérazine, 3-benzyl-6-iso-propyl-2,5-dicétopipérazine, 3-benzyl-6-(4-aminobutyl)-2,5-dicétopipérazine, 3,6-di(benzyl)-2,5-dicétopipérazine, 3,6-di(4-hydroxybenzyl)-2,5-dicétopipérazine, 3,6-di(4-(benzyloxy)benzyl)-2,5-dicétopipérazine, 3-benzyl-6-(4-imidazolyl)méthyl-2,5-dicétopipérazine, 3-benzyl-6-méthyl-2,5-dicétopipérazine, 3-benzyl-6-(2-(benzyloxycarbonyl)éthyl)-2,5-dicétopipérazine ou leurs mélanges.
  12. Composition selon l'une des revendications précédentes,
    caractérisée en ce que l'eau est contenue en une quantité totale comprise entre 4 et 70 % en poids.
  13. Procédé permettant le traitement de substrat, comprenant les étapes de procédé consistant à
    (a) fournir un bain aqueux en mélangeant 0,5 L à 40,0 L d'eau avec 0,5 à 100 g d'une composition selon l'une des revendications 1 à 12, et
    (b) mettre en contact au moins un textile avec le bain aqueux préparé selon (a).
  14. Procédé permettant la préparation d'une composition tensioactive solide selon l'une des revendications 1 à 12, caractérisé en ce qu'une composition liquide contenant au moins un composé organique comportant une masse moléculaire < 1000 g/mol, une solubilité dans l'eau inférieure à 0,1 g/L (20 °C, pH 7) et une structure contenant
    a) au moins deux groupes choisis parmi -OH, -NH-, ou des mélanges de ceux-ci, et
    b) au moins un motif constitutif carbocyclique comportant au moins deux liaisons doubles endocycliques, en particulier au moins un motif constitutif aromatique carbocyclique,
    et
    c) au moins un autre motif constitutif cyclique qui présente au moins deux groupes carbonyle
    est d'abord amenée, en présence d'eau et de 0,1 à 70 % en poids d'un tensioactif et éventuellement d'additifs facultatifs, à une température supérieure à la température de transition sol-gel de la composition liquide, et ensuite la composition liquide chauffée est introduite dans un moule, de préférence dans une cavité d'un moule en auge, et est refroidie dans ledit moule en dessous de la température de transition sol-gel en formant un corps moulé solide et viscoélastique.
EP19702201.5A 2018-02-06 2019-01-21 Composition tensioactive viscoélastique solide Active EP3749738B1 (fr)

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PCT/EP2019/051336 WO2019154612A1 (fr) 2018-02-06 2019-01-21 Composition tensioactive viscoélastique solide

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DE102018209002A1 (de) 2018-06-07 2019-12-12 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Fließgrenze
EP4017957B1 (fr) * 2019-08-21 2023-03-29 Unilever IP Holdings B.V. Composition détergente solide
DE102023212739A1 (de) * 2023-12-14 2025-06-18 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittelformkörper

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CA1190695A (fr) 1981-05-14 1985-07-16 George J. Stockburger Agent anionique pour le traitement des textiles
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ATE73150T1 (de) 1984-12-21 1992-03-15 Procter & Gamble Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen.
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
GB8617255D0 (en) 1986-07-15 1986-08-20 Procter & Gamble Ltd Laundry compositions
GB8629936D0 (en) 1986-12-15 1987-01-28 Procter & Gamble Laundry compositions
US4721580A (en) 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
DE68925765T2 (de) 1988-08-26 1996-10-02 Procter & Gamble Schmutzabweisende Mittel mit von Allylgruppen abgeleiteten sulphonierten Endgruppen
DE4001415A1 (de) 1990-01-19 1991-07-25 Basf Ag Polyester, die nichtionische tenside einkondensiert enthalten, ihre herstellung und ihre verwendung in waschmitteln
DE10000223A1 (de) 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
AU2002256304A1 (en) 2001-04-20 2002-11-05 Srilalitha Belur Compositions for delivery of compounds to cells and methods of use
DE102008051799A1 (de) 2008-10-17 2010-04-22 Henkel Ag & Co. Kgaa Stabilisierung von Mikrokapsel-Slurries
WO2011112886A1 (fr) * 2010-03-12 2011-09-15 The Procter & Gamble Company Compositions détergentes fluides comprenant un gélifiant di-amido et leurs procédés de fabrication
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