EP3749738A1 - Composition tensioactive viscoélastique solide - Google Patents

Composition tensioactive viscoélastique solide

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Publication number
EP3749738A1
EP3749738A1 EP19702201.5A EP19702201A EP3749738A1 EP 3749738 A1 EP3749738 A1 EP 3749738A1 EP 19702201 A EP19702201 A EP 19702201A EP 3749738 A1 EP3749738 A1 EP 3749738A1
Authority
EP
European Patent Office
Prior art keywords
group
alkyl group
alkyl
surfactant
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19702201.5A
Other languages
German (de)
English (en)
Inventor
Anna KLEMMER
Peter Schmiedel
Filiz Yapici
Boris Nachtsheim
Dominik Göbel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3749738A1 publication Critical patent/EP3749738A1/fr
Pending legal-status Critical Current

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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

  • 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.
  • detergents are in solid form (for example as powders or tablets) or in liquid form (or else as flowing gel). In particular, liquid washing or
  • Solid substrate treatment agents have the advantage that, in contrast to liquid substrate treatment agents, they do not require preservatives and contain the same
  • Ingredients can be more stable incorporated.
  • Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained.
  • Substrate treatment agents such as detergent pouches or dishwashing tablets, for machine substrate treatment accustomed 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, for example, that leakages in the sachet of the portion cause the liquid composition to run out.
  • Disposable portions in water-soluble bags enjoy popularity with the consumer also because of the attractive appearance of the disposable portion.
  • the appearance of the dosage form is becoming more important.
  • a good appearance is one of the reasons for choosing a product.
  • transparent products are perceived by the consumer as visually appealing.
  • Textile cleaning used solid surfactant compositions are usually opaque. It is therefore also an object to translucent to transparent solid surfactant compositions
  • the object of the invention to provide solid-form surfactant compositions, in particular as a single-use portion in the form of a particulate shaped body, which dissolve readily in water or can be dispersed therein upon contact with water.
  • surfactant compositions with a storage modulus of 40,000 to 800,000 Pa known.
  • the viscoelastic surfactant compositions disclosed therein are liquid crystalline
  • Another object was thus to provide solid-form surfactant compositions which have a viscoelastic behavior independently of the phase behavior of the surfactants used.
  • a first subject of the invention is therefore a viscoelastic, festförmige
  • Surfactant composition especially as a washing or cleaning agent, containing based on their total weight
  • endocyclic double bonds in particular at least one carbocyclic, aromatic structural unit,
  • a viscoelastic, solid surfactant composition in particular as a washing or cleaning agent, based on their total weight
  • endocyclic double bonds in particular at least one carbocyclic, aromatic structural unit,
  • 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 (each at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz) and the memory module in the frequency range between 10 3 Hz and 10 2 Hz is at least twice greater than the loss modulus. More preferably, the composition has a storage modulus in a range of 10 5 Pa to 10 7 Pa.
  • the storage modulus is at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus (in each case at 20 ° C., a deformation of 0.1%). and a frequency of 1 Hz). All definitions and preferred embodiments below, unless otherwise defined, apply equally to the first embodiment and the second embodiment.
  • the viscoelastic, solid surfactant composition combines all the advantages of a liquid composition with its solid form, providing an aesthetic product form with a good dissolution profile in the context of textile treatment with an outstanding performance profile on the substrate.
  • the viscoelastic solid surfactant composition of the present invention is storage and dimensionally stable.
  • the said viscoelastic, solid surfactant composition exhibits almost no syneresis even after prolonged storage.
  • a substance e.g., a composition
  • a substance is solid according to the definition of the invention when in the solid state at 20 ° C and 1013 mbar.
  • a fabric e.g., a composition
  • a fabric is viscoelastic and solid when at 20 ° C the storage modulus of the fabric is greater than the loss modulus present.
  • the storage modulus and the loss modulus are notoriously familiar to the person skilled in the art (see Christopher W. Macosco, "Rheology Principles, Measurements and Applications", VCH, 1994, pp.
  • Rotationsrheometer for example, TA Instruments, type AR G2, Malvern "Kinexus", carried out using a cone-plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C. This is
  • each unit: Pa was carried out with the equipment described above in an experiment with oscillating deformation.
  • the linear viscoelastic region is first determined in a stress sweep experiment.
  • the shear stress amplitude increased.
  • the modules G 'and G are in one
  • plotted log log plot On the x-axis can optionally the
  • Shear stress amplitude or the (resulting) deformation amplitude can be plotted.
  • the memory module G ' is below a certain shear stress amplitude or Deformation amplitude constant, above it collapses.
  • the break point is suitably determined by applying tangents to 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 e.g. moved between 0.001 Hz and 100 Hz at a constant deformation amplitude.
  • Deformation amplitude must be chosen so that it is in the linear range, i. below the o.g. critical deformation lies. In the case of the invention
  • Compositions has a deformation amplitude of 0.1% proved suitable.
  • the modules G 'and G are plotted against the frequency in a log-log plot.
  • a substance e.g., a composition
  • a substance is liquid according to the definition of the invention when in the liquid state at 20 ° C and 1013 mbar.
  • a chemical compound is an organic compound when the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen.
  • a chemical compound is, inversely to the definition of the organic compound, an inorganic compound when 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 completely formed 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.
  • Hydrocarbons i.e. aromatic compounds with fused ring systems are explicitly covered by this definition.
  • weight-average molar masses M w which can be determined in principle by means of gel permeation chromatography with the aid of an RI detector, wherein the measurement is expediently carried out against an external standard.
  • a "surfactant-containing liquor” in the context of the invention is a liquid preparation obtainable by use of a surfactant-containing dilution with at least one solvent (preferably water) for the treatment of a substrate.
  • a substrate tissue or textiles (such as clothing), as well as hard surfaces (such as dishes, ceramics, plastic, metal) come into question.
  • the surfactant compositions according to the invention are preferred for providing a surfactant-containing liquor used in the context of mechanical cleaning processes, such as those performed by a washing machine for textiles or a dishwasher.
  • the surfactant compositions according to the invention can preferably also be used as cleaners for hard surfaces, such as ceramics, toilets or glass.
  • the surfactant compositions according to the invention can be used in particular as toilet cleaners.
  • the surfactant-containing liquor is here preferably applied by a toilet bowl on the toilet rim on the rinse or glued directly to the inner surface of the toilet bowl and distributed over the rinse.
  • At least one refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient.
  • at least one inorganic base means, for example, one or more different inorganic bases, i. one or more different types of inorganic bases. The amounts given, together with quantities, refer to the total amount of the corresponding type of ingredient.
  • the viscoelastic, solid surfactant composition according to the invention is preferably transparent or translucent.
  • a mixture according to the invention in the spectral range between 380 nm and 780 nm has a residual light power related to the reference measurement
  • the transparency of the surfactant composition according to the invention can be determined by various methods.
  • the nephelometric turbidity unit (NTU) is often used as a measure of transparency. It is a e.g. in the
  • the HACH Turbidimeter 2100Q turbidimimeter from Hach Company, Loveland, Colorado (USA) is used with the calibration probes StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU). , all can also be ordered from Hach Company.
  • the measurement is in a 10 ml cuvette with cap filled with the composition to be examined and the measurement is carried out at 20 ° C.
  • the surfactant compositions of the invention have an NTU (at 20 ° C) of at most 120, more preferably at most 1 10, more preferably at most 100, most preferably at most 80.
  • the transparency of the solid-state agents according to the invention was determined by a transmission measurement in the visual light spectrum over a wavelength range from 380 nm to 780 nm at 20 ° C.
  • a reference sample water, deionized
  • a photometer Messrs. Specord S 600 from Analytik Jena
  • a cuvette which is transparent in the spectrum to be examined (layer thickness 10 mm).
  • 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 at least 50%, very particularly preferably at least 60%.
  • Surfactant composition has a transmission (at 20 ° C) of at least 30% (in particular of at least 40% more preferably of at least 50%, more preferably of at least 60%) and an NTU value (at 20 ° C) of at most 120 (more preferably at most 1) 10, more preferably at most 100, more preferably at most 80).
  • the viscoelastic, solid-form surfactant composition according to the invention contains, based on its total weight, a total amount of from 0.1 to 70% by weight of surfactant.
  • Suitable surfactants 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 from 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, most preferably from From 20 to 70% by weight, more preferably from 20 to 65% by weight, more preferably from 20 to 60% by weight, most preferably from 25 to 70 Wt .-%, more preferably from 25 to 65 wt .-%, more preferably from 25 to 60 wt .-%, further preferably from 30 to 70 wt .-%, more preferably from 30 to 65 wt .-%, 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
  • the surfactant composition contains at least one anionic surfactant and optionally additionally at least one nonionic surfactant.
  • Dishwashing agents in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt .-%, in particular 0.2 to 4.0 wt .-%, of at least one surfactant.
  • An inventively preferred viscoelastic, solid-form surfactant composition 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 which are suitable as dishwashing agents contain in each case, based on the weight of the composition, 0 to 1% by weight, in particular 0 to 0.5% by weight, particularly preferably 0 to 0, 25% by weight, anionic surfactant.
  • anionic surfactant when the surfactant composition of the invention contains anionic surfactant and is used as a laundry detergent, it is preferred that based on the total weight of the composition, anionic surfactant be present in a total amount of from 5 to 70% by weight, more preferably from 5 to 60% by weight, more preferably from 10 to 70 wt .-%, in particular 10 to 60 wt .-%, particularly preferably from 10 to 40 wt .-%, more preferably from 25 to 40 wt .-%, is contained.
  • surfactant composition Regardless of the field of application of the surfactant composition according to the invention, preference is given to using sulfonates and / or sulfates as the anionic surfactant.
  • surfactants of the sulfonate type are preferably C9 -i3-alkylbenzenesulfonates,
  • Olefinsulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • Particularly preferred surfactant compositions according to the invention in particular
  • R ' and R " are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C atoms, and Y + is a monovalent cation or the nth part of an N-valent cation (especially Na + ).
  • Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of
  • Sulfuric acid half esters of C 12 -18 fatty alcohols for example from coconut fatty alcohol,
  • Ci2-Ci6-alkyl sulfates and Ci 2 -Ci5-alkyl sulfates and Ci 4 -Ci5-alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the Schwefelkladmonoester the ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C7 2i alcohols such as 2-methyl-branched C9-11- alcohols containing on average 3.5 mol ethylene oxide (EO) or Ci2-is- Fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • anionic surfactants and the soaps may be in the form of their sodium, potassium or
  • the anionic surfactants are in the form of their ammonium salts.
  • Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.
  • Surfactant composition in particular as a laundry detergent, a monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C9 -i3-alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.
  • a preferred surfactant composition of the invention contains at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefin-sulfonates, C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
  • anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefin-sulfonates, C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
  • Surfactant composition in particular as a washing or cleaning agent, at least one nonionic surfactant.
  • the at least one nonionic surfactant may be any known nonionic surfactant suitable for the purpose of this invention.
  • the surfactant composition contains at least one nonionic surfactant.
  • Dishwashing agents in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt .-%, in particular 0.2 to 4.0 wt .-%, of at least one nonionic surfactant.
  • Textile detergents in particular for use in a washing machine, each contain, based on the weight of the composition, 1, 0 to 25 wt .-%, preferably 2.5 to 20.0 wt .-%, more preferably 5.0 to 18.0 Wt .-%, of at least one nonionic surfactant.
  • the at least one nonionic surfactant may be any known nonionic surfactant suitable for the purpose of this invention.
  • compositions as nonionic surfactant at least one fatty alcohol alkoxylate represented by the following formula (T-2),
  • R ' is a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical
  • XO is independently an ethylene oxide (EO) or propylene oxide (PO) grouping and m is an integer from 1 to 50.
  • R ' is a linear or branched, substituted or unsubstituted alkyl radical.
  • Embodiment of the present invention is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and especially having 10 to 19 carbon atoms.
  • Preferred radicals R ' are selected from decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred.
  • radicals R ' are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.
  • XO of the formula (T-2) is an ethylene oxide (EO) or propylene oxide (PO) grouping,
  • m of the formula (T-2) is an integer of 1 to 50, preferably 2 to 20, and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • Surfactant composition may include mixtures of nonionic surfactants having different degrees of ethoxylation.
  • particularly preferred fatty alcohol alkoxylates are those of the formula (T-3)
  • Such fatty alcohol ethoxylates are available under the brand names 45-7 Dehydol LT7 ® (BASF) Lutensol ® A07 (BASF) Lutensol ® M7 (BASF), and Neodol ® (Shell Chemicals).
  • the surfactant compositions according to the invention contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol.
  • Preferred ethoxylated alcohols include, for example, Ci 2 -i 4 alcohols containing 3 EO or 4 EO, Cs-n-alcohol with 7 EO, Cs alcohols containing 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 C12-14 alcohol with 3 EO and Ci2-is-alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, in particular as automatic dishwashing detergents. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants which have been obtained from C 6-20 monohydroxyalkanols or C 6-2 o -alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol, used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20
  • Carbon atoms (C 16-20 alcohol), preferably a C-is-alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide.
  • C 16-20 alcohol preferably a C-is-alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated 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 machine dishwashing detergents, have been found in the context of the present invention to be the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 1 24 alkyl or-alkenyl stands for a straight-chain or branched, saturated or inclusion as polyunsaturated C6; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6 ,
  • 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 may vary depending on the origin of the alcohol. When native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 carbon atoms. Atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 1 1 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable.
  • nonionic surfactants in particular for automatic dishwashing detergents, are nonionic surfactants of the general formula (T-5)
  • Nonionic surfactants of the general formula (T-6) are preferred here.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.
  • Preferred nonionic surfactants here are, in particular for automatic dishwashing detergents, those of the general formula (T-8)
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6- 24 -alkyl or -alkenyl radical
  • R 2 is hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, A ', A "and A'" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ),
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • inventive preparations can be significantly improved and indeed compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals
  • stability of the enzymes optionally additionally present in the surfactant compositions according to the invention can be markedly improved.
  • Preferred end-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula (T-10), are preferred, in particular for machine dishwashing detergents.
  • R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, wherein n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y CH 2 CH (O) R 2 ,
  • 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 one
  • the group of these non-ionic surfactants include for example the C2-26 fatty alcohol (PO) i- (EO) -2- i5 40 hydroxyalkyl ethers, in particular the Cs -io fatty alcohol (PO) i- (EO) 22 -2-hydroxydecylether ,
  • R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH3) 2, but preferably -CFh
  • nonionic surfactants in particular for machine dishwashing detergents, are the end-capped poly (oxyalkylated) nonionic surfactants of the formula RO [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, iso-propyl, n Is 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. If the value x> 2, each R 3 in the above formula
  • 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.
  • R 3 H, -CF or -CH 2 CH 3 are particularly preferred.
  • 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 may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • R 1 0 [CH 2 CH (R 3 ) O] X CH 2 CH (OH) CH 2 0R 2 simplified.
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) W -R 2 have proved to be particularly effective, in which
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6- 24 -alkyl or -alkenyl radical
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3), preferably CH 2 CH 2 , and
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
  • the group of these non-ionic surfactants include for example the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO) 22 -2-C4 hydroxydecylether and 22 fatty alcohol (EO) 40 -80-2-hydroxyalkyl ether.
  • the surfactant composition of the present invention may contain, as a nonionic surfactant, amine oxide.
  • amine oxide are in principle all established in the art for this purpose amine oxides thus compounds having the formula R 1 R 2 R 3 NO, wherein each R 1 , R 2 and R 3 independently of the other an optionally substituted hydrocarbon chain with 1 to 30 carbon atoms, can be used.
  • Particularly preferred amine oxides are those in which R 1 is alkyl of 12 to 18 carbon atoms and R 2 and R 3 are each independently alkyl of 1 to 4 carbon atoms, especially alkyl dimethylamine oxides of 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
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • Indicating oligoglycosides is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants 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 having 1 to 4 carbon atoms in the alkyl chain.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • alkoxylated fatty acid alkyl esters of the formula R 3 CO- (OCH 2 CHR 4 ) w OR 5 ,
  • R 3 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 4 is hydrogen or methyl
  • R 5 is linear or branched alkyl radicals having 1 to 4 carbon atoms and w is 1 to 20,
  • compositions of the invention described herein may also contain several of the nonionic surfactants described above.
  • viscoelastic, solid-form surfactant compositions in particular as textile detergents, contain in each case based on the total weight a total amount of
  • Very particular preferred viscoelastic, solid-form surfactant compositions according to the invention contain, in addition to water and said organic compound of component (ii), at least one surfactant combination as described below for compositions (A) to (D):
  • anionic surfactant From 10 to 60% by weight of at least one anionic surfactant, wherein at least one C9 -i3-alkylbenzenesulfonate is present as the anionic surfactant, and
  • nonionic surfactant containing as nonionic surfactant at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol.
  • EO ethylene oxide
  • anionic surfactant 10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least 5 to 60 wt .-% of at least one C9 -i3-alkylbenzenesulfonate is contained, and
  • nonionic surfactant From 2 to 35% by weight of at least one nonionic surfactant, wherein as nonionic surfactant at least 2 to 35% by weight of at least one alkoxylated alcohol having 8 to 18
  • (C) Viscoelastic, solid-form surfactant composition containing, as surfactant, in each case at least in each case a total amount of, based on the total weight of the composition - 25 to 40 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least one C9 -i3-alkylbenzenesulfonate is contained, and
  • nonionic surfactant 18 to 28 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included.
  • EO ethylene oxide
  • anionic surfactant at least 25 to 40 wt .-% of at least one C9 -i3-alkylbenzenesulfonate is contained, and
  • nonionic surfactant 18 to 28 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant at least 18 to 28 wt .-% of at least one alkoxylated alcohol having 8 to 18
  • the amounts of the individual surfactant components are, of course, to be selected within the given quantitative ranges of the individual surfactant components such that the predetermined total amount of surfactant is maintained.
  • the viscoelastic, solid-form surfactant composition according to the invention (in particular as a laundry 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 having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms.
  • the polyamine has at the ends (terminus and / or side chains) primary amino functions and internally preferably both secondary and tertiary amino functions; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.
  • 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 has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol.
  • the N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number.
  • PEI polyethyleneimine
  • the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 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 attached to any existing propoxy and N atoms which do not carry 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 reaction of polyamines with propylene oxide (abbreviated to PO) 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, especially 15 to 30.
  • the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine may 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 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 secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function.
  • a most 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
  • Polyamines obtainable by reaction of polyamines with ethylene oxide and
  • propylene oxide Be with ethylene oxide and propylene oxide
  • the proportion of propylene oxide in the total amount of the alkylene oxide is preferably 2 mol% to 18 mol%, especially 8 mol% to 15 mol%.
  • the viscoelastic, solid-form surfactant composition according to the invention preferably additionally contains, based on its weight, polyalkoxylated polyamines in a total amount of from 0.5 to 12% by weight, in particular from 5.0 to 9.0% by weight.
  • the viscoelastic, solid-form surfactant composition according to the invention in particular as a laundry detergent, additionally contains at least one soil-release agent.
  • Soil release agents are often referred to as “soil release” agents or because of their ability to render the treated surface, preferably textiles, soil repellent, "soil repellents.” Because of their chemical similarity to polyester fibers, particularly effective soil release agents Fabrics made of other materials which can show the desired effect are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil release polymers of the type mentioned, as well as their use in laundry detergents for textiles, have been known for a long time.
  • European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer.
  • European Patent EP 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. From the European patent EP 241 985, polyesters are known, 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 with to C 4 alkyl groups End phenomenon are.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0, 6 to 0.95.
  • 4 alkyl or acyl groups end-capped polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units are at least in part by Ci- known from European Patent Application EP 272 033rd European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • European Patent Application EP 272 033rd European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • Patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C 2-4 glycol units.
  • Surfactant composition at least one soil release-capable polyester, comprising the structural units E-1 to E-III or E-1 to E-IV,
  • a, b and c independently of one another each represent a number from 1 to 200
  • d, e and f independently of one another each represent a number from 1 to 50
  • g is a number from 0 to 5
  • Ph is a 1,4-phenylene radical
  • sPh is a 1, 3-phenylene radical substituted in position 5 by a group -SO3M,
  • M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium, wherein the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl- or C 2 -C 10 -hydroxyalkyl radicals or any mixtures thereof, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group,
  • R 7 is a linear or branched C 1 -C 30 -alkyl group or a linear or branched C 2 -C 30 -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C 6 -C 30 -aryl group or a C 6 -C 30 -arylalkyl group, and
  • Polyfunctional unit for a unit having 3 to 6 functional groups capable of esterification reaction for a unit having 3 to 6 functional groups capable of esterification reaction.
  • Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester,
  • Alkylene glycols optionally polyalkylene glycols (at a, b and / or c> 1) and on one side
  • from 1 to 50 units (E1) may be contained per polymer chain.
  • unit (E-II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (E-II) may be present.
  • groups can be acid, alcohol, ester, anhydride or
  • Gallic acid more preferably 2,2-dihydroxymethylpropionic serve.
  • polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used.
  • These may also be polybasic 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 ( Trimesithklare) act.
  • the proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and more preferably up to 3% by weight.
  • the polyesters containing the structural units (El), (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, the number average molecular weight being determined can be determined by size exclusion chromatography in aqueous solution using calibration using 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 from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol. According to the invention are preferred as part of the particle of the second kind solid
  • Polyester the softening points above 40 ° C, used; they preferably have a softening point between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C, and most preferably between 100 ° C and 120 ° C.
  • the synthesis of the polyesters can be carried out by known processes, for example by first heating the abovementioned components with the addition of a catalyst at atmospheric pressure and then the required
  • the viscoelastic, solid-form surfactant composition according to the invention may additionally comprise at least one enzyme as 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 which 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, .beta.-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.
  • proteases amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • subtilisin type those of the subtilisin type are preferable.
  • 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 subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from the company Genencor, which was sold under the
  • amylases which can be used according to the invention are the a-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents or cleaners.
  • the B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and TermamyKDultra, from Genencor under the name Purasta DOxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • amyloliquefaciens a-amylase is sold by Novozymes under the name BAN®, and variants derived from the B. stearothermophilus a-amylase under the names BSG® and Novamyl®, also from the company Company Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the a-amylase from Aspergillus niger and A.
  • oryzae available under the trade name Fungamyl® from the company Novozymes are suitable.
  • Further advantageously usable commercial products are, for example, the amylase-LT®, as well as Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter likewise of the amylase-LT®, as well as Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter likewise of the
  • lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, 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®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • Lipases which are likewise useful are sold by 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® By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Lipase.RTM Lipase.RTM.
  • Lipomax.RTM Originally sold by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.
  • cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects, in particular in portions for textile washing.
  • performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (tissue effect) or to the exercise of a "stone-washed" effect.
  • cleaning performance cleaning performance
  • anti-redeposition effect or graying inhibition anti-redeposition effect or graying inhibition
  • tissue effect tissue effect
  • a useful fungal, endoglucanase (EC ) -rich cellulase preparation, or their further developments is from the company
  • Novozymes under the trade name Celluzyme® offered.
  • the products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800.
  • Other usable commercial products this company is Cellusoft®, Renozyme® and Celluclean®.
  • Also usable are, for example, the 20 kD-EG from Melanocarpus available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®.
  • Further commercial products of AB Enzymes are Econase® and Ecopulp®.
  • Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp.
  • hemicellulases include, for example, mannanases, xanthanlyases,
  • Xanthanases xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes and ⁇ -glucanases.
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
  • Hemicellulases which are particularly preferred according to the invention are mannanases, which are available, for example, under the trade name Mannaway® from the
  • pectin-destroying enzymes are likewise counted as enzymes with the designations pectinase, pectate lyase, pectin esterase,
  • Exopolygalacturonosidase or Exopolygalacturanosidase examples are, for example, under the name Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes, and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • the viscoelastic, solid surfactant composition of the present invention preferably contains enzymes in total amounts of 1 x 10 8 to 5 percent by weight based on active protein.
  • the enzymes are present in a total amount of from 0.001 to 2 wt.%, More preferably from 0.01 to 1.5 wt.%, Even more preferably from 0.05 to 1.25 wt.%, And most preferably from 0.01 to 0.5 wt .-% included.
  • pH adjuster preferably in laundry detergents
  • perfume preferably in laundry detergents
  • dye transfer inhibitor or mixtures thereof.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.
  • phosphates also polyphosphates
  • the use of phosphates is largely or completely omitted.
  • Viscoelastic, solid surfactant composition in this embodiment preferably contains less than 5 wt%, more preferably less than 3 wt%, most preferably less than 1 wt%, of phosphate (s). Particularly preferred is the invention
  • Surfactant composition in this embodiment completely phosphate-free, i. the
  • Compositions contain less than 0.1% by weight of phosphate (s).
  • the builders include in particular carbonates, citrates, phosphonates, organic acids, and organic acids.
  • the proportion by weight of the total builders in the total weight of the viscoelastic, solid composition according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight for dishwashing detergents.
  • Suitable organic builders according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which have more than one, in particular two to eight
  • Acid functions, preferably two to six, in particular two, three, four or five
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups.
  • 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, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA),
  • NTA nitrilotriacetic acid
  • glutamine-N glutamine-N
  • N-diacetic acid also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA
  • Methylglycinediacetic acid and its 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 having a multiplicity of (in particular greater than 10) carboxylate functions in the
  • Macromolecule Polyaspartates, polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component.
  • an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred surfactant compositions according to the invention contain as one of their essential builders one or more salts of citric acid, ie citrates. These are in the surfactant compositions according to the invention (especially for textile washing) preferably in a proportion of 0.3 to 10 wt .-%, in particular from 0.5 to 8 wt .-%, especially from 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.
  • Citric acid are present in the surfactant compositions according to the invention (in particular for the cleaning of hard surfaces, in particular for dishwashing), preferably in a proportion of from 2 to 40% by weight, in particular from 5 to 30% by weight, especially from 7 to 28% by weight. %, particularly preferably 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total weight of the composition.
  • the viscoelastic, solid-form surfactant compositions according to the invention may contain in particular phosphonates as further builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance.
  • Aminoalkanphosphonate are preferably
  • Ethylenediamine tetramethylene phosphonate Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs in question.
  • Phosphonates are present in viscoelastic, solid-colored surfactant compositions according to the invention preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight. %, in each case based on the total weight of the composition.
  • Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities.
  • inventive surfactant compositions in particular detergents or cleaners, preferably dishwashing agents, more preferably automatic dishwashing detergents, are characterized in that in addition to citrate and (hydrogen) carbonate and optionally phosphonate they contain at least one further phosphorus-free builder.
  • the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA),
  • Glutamic acid diacetate GLDA
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • a particularly preferred combination is, for example, citrate,
  • the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules.
  • MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder
  • organic builders polymeric polycarboxylates are also suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid,
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.
  • the viscoelastic, solid-form surfactant compositions according to the invention can furthermore comprise, as builder, crystalline layer-form silicates of the general formula NaMSixO 2x + iy H2O, in which M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 ⁇ D: S1O 2 of from 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 Delayed and have secondary washing properties.
  • amorphous sodium silicates having a modulus Na 2 ⁇ D: S1O 2 of from 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
  • An optical brightener is preferably stilbenedisulfonic acids from the substance classes of distyrylbiphenyls, the stilbenes, the 4,4 'diamino-2,2', coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of the benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocyclic substituted pyrene derivatives, and mixtures thereof.
  • optical brighteners include disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate (available, for example, as Tinopal® DMS from BASF SE), disodium 2,2 '.
  • the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole.
  • Color transfer inhibiting polymers include polyvinylpyrrolidone (PVP),
  • Polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI),
  • polyvinylpyrrolidone PVP
  • polyvinylimidazole PVI
  • copolymers of vinylpyrrolidone and vinylimidazole PVP / PVI
  • 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 available.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000.
  • the viscoelastic, solid-form surfactant composition according to the invention contains incorporated solid particles (in the US Pat
  • dispersed solid particles are 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-form surfactant composition according to the invention and are present as a separate phase. These particles are used in the preparation of the viscoelastic
  • the solid particles are preferably selected from polymers, pearlescent pigments,
  • Microcapsules, speckles or mixtures thereof are Microcapsules, speckles or mixtures thereof.
  • microcapsules include any type of capsule known to those skilled in the art, but in particular core-shell capsules and matrix capsules.
  • Matrix capsules are porous shaped bodies that have a structure similar to a sponge.
  • Core-shell capsules are shaped bodies having a core and a shell.
  • Suitable microcapsules are those capsules which have an average diameter Xso, 3 (volume average) of from 0.1 to 200 ⁇ m, preferably from 1 to 100 ⁇ m, more preferably from 5 to 80 ⁇ m, particularly preferably from 10 to 50 ⁇ m and in particular from 15 to 40 pm.
  • the mean particle size diameter X 50.3 is determined by sieving or by means of a particle size analyzer Camsizer from Retsch.
  • microcapsules of the invention preferably contain at least one active ingredient, preferably at least one perfume. These preferred microcapsules are perfume microcapsules.
  • the microcapsules have a semipermeable capsule wall (shell).
  • a semipermeable capsule wall is a capsule wall which is semipermeable, ie it releases small quantities of the capsule core continuously over time, without the capsule having to be filled, for example. was damaged or opened by friction. Such capsules continuously continue to set small amounts of the capsule drug, e.g. Perfume, free.
  • the microcapsules have an impermeable shell.
  • An impermeable shell in the sense of the present invention is a capsule wall which is substantially impermeable, that is to say releases the capsular core only by damaging or opening the capsule.
  • Such capsules contain in the capsule core significant amounts of at least one fragrance, so that when damaged or when opening the capsule a very intense fragrance is provided.
  • the resulting scent intensities are usually so high that lower amounts of the microcapsules can be used to achieve the same scent intensity as conventional microcapsules.
  • Microcapsules with impermeable shell Through the use of both capsule types, a significantly improved fragrance intensity can be provided over the entire laundry cycle.
  • composition according to the invention may also contain two or more different microcapsule types with semipermeable or impermeable shell.
  • materials for the shell of the microcapsules are usually high molecular weight
  • Epoxy resins and others Preferably serves as a wall material, ie as a shell, melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer.
  • a wall material ie as a shell, melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer.
  • Preferred melamine-formaldehyde microcapsules are prepared in which 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
  • 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, sulfonic acid-containing water-soluble polymers containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and polymers of N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styre
  • At least one cationic polymer of polyquaternium-1, polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10 is suitable as cationic polymer for coating the microcapsules , Polyquaternium-1, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-19, Polyquaternium-20,
  • Polyquaternium-86th Very particular preference is given to polyquaternium-7.
  • the polyquaternium nomenclature of the cationic polymers used in the context of this application is taken from the declaration of cationic polymers according to the International Nomenclature of Cosmetic Ingredients (INCI Declaration) of cosmetic raw materials.
  • Preferably usable microcapsules have average diameters Xso, 3 in the range of 1 to 100 pm, preferably from 5 to 95 pm, in particular from 10 to 90 pm, for example from 10 to 80 pm.
  • the shell of the microcapsules surrounding the core or (filled) cavity preferably has an average thickness in the range from 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 shine. Pearlescent pigments consist of thin leaflets that have a high refractive index and partially reflect the light and are partially transparent to the light. The nacreous gloss is produced by interference of the light striking the pigment (interference pigment). Pearlescent pigments are usually thin flakes of the above material, or contain the o.g. Material as thin multilayer films or as parallel arranged components in a suitable carrier material.
  • the pearlescent pigments which can be used according to the invention are either natural
  • Pearlescent pigments such as e.g. Fischsilber (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 mica-based pearlescent pigments as well as mica / metal oxide.
  • the latter pearlescent pigments are mica, which have been provided with a metal oxide coating.
  • Mica-based and mica / metal oxide-based pearlescent pigments are preferred according to the invention.
  • Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. For the production of
  • Suitable metal oxides Cr 2 Ü3 and Fe include T1O2, 2 03.
  • interference pigments as well as color luster pigments according to the invention obtained as pearlescent pigments.
  • these pearlescent pigment types also have color effects.
  • the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which does not derive from a metal oxide.
  • the grain size of the pearlescent pigments preferably used is preferably at a mean diameter Xso, 3 (volume average) between 1 .0 and 100 .mu.m, more preferably between 10.0 and 60.0 pm.
  • speckles are macroparticles, in particular macrocapsules, which have an average diameter Xso, 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 well as the production of particles with these matrix-forming materials.
  • An exemplary matrix-forming material is alginate.
  • alginate-based speckles is an aqueous alginate solution, which if necessary, in addition to the entrapped drug or the
  • the surfactant compositions according to the invention in particular as dishwashing compositions, in a preferred embodiment contain as further constituent at least one zinc salt as glass corrosion inhibitor.
  • the zinc salt may be an inorganic or to act as an organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of
  • 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 of 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 preferably present in surfactant compositions according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the composition.
  • Salts in particular the zinc salts
  • the viscoelastic solid surfactant composition of the present invention necessarily contains at least one said organic compound of component (ii).
  • such surfactant compositions are preferably suitable in which the carbocyclic structural unit b) is selected from at least one optionally substituted aryl group, in particular an optionally substituted phenyl group. 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 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
  • Heteroaryl group a Hetroaryl- (Ci-C3) -alkyl group, a (Ci-C 4 ) -Hydroxyalkyl distr, a (Ci-C 4 ) -Aminoalkyl distr, a carboxy (Ci-C3) -alkyl distr.
  • the further cyclic structural unit c) is different from the carbocyclic structural unit b).
  • the further cyclic structural unit c) binds covalently either directly or via a divalent, bridging structural unit (preferably via (C 1 -C 4 ) -alkanediyl) to the carbocyclic structural unit b).
  • the carbon atoms of the at least two carbonyl groups from the further cyclic structural unit c) are ring-forming.
  • the further cyclic structural unit c) is particularly preferably 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. In this case, it has again turned out to be particularly preferred if the surfactant compositions according to the invention (based in each case on the total weight of the composition) of organic compound of component (ii) in a total amount of at least 0.55 wt.%, In particular of at least 0.7 wt. -%, particularly preferably of at least 0.8 wt .-% contains.
  • organic compound of component (ii) in a total amount of 0.5 to 3.0 wt.%, In particular from 0.7 to 2.5 wt .-%, most preferably from 0.8 to 2.0% by weight, most preferably from 0.85 to 1.5% by weight.
  • compositions according to the invention therefore comprise as component (ii) at least one 2,5-diketopiperazine compound of the formula (I)
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a
  • Aminocarbonyl- (C 1 -C 4) -alkyl group an N- (C 1 -C 4 ) -alkylaminocarbonyl- (C 1 -C 4 ) -alkyl group, an N, N-di (C 1 -C 4 ) -alkyl) aminocarbonyl- (C 1 -C 4 ) -alkyl group; C 4 ) alkyl group, an N- (C 2 -C 8) -acylaminocarbonyl (C 1 -C 4 ) -alkyl group, an N, N- (C 2 -C 8) -diacylaminocarbonyl- (C 1 -C 4 ) -alkyl group, an N- (C 2 -C 8) -Acyl-N- (C 1 -C 4 ) -alkylaminocarbonyl- (C 1 -C 4 ) -alkyl group, an N- (aryl- (C
  • Substituted hydrogen are preferably all defined under the definitions of R 5 and R 1 according to formula (I) radicals other than a hydrogen atom, in particular a hydroxy group, an amino group, a (Ci-C6) alkyl group, a (C2 -C6) alkenyl group, a (C2-C6) acyl group, a (C2-C6) acyloxy group, a (Ci-C6) alkoxy group, an amino group, a (C2-C6) acylamino group, a (Ci-C6 ) -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, a heteroaryl group, a heteroaryl- (C 1 -C 3) - alkyl group,
  • alkyl group (or an alkyl structure fragment of a more complex group) is according to the invention a group selected from linear alkyl group of branched alkyl group or Cyclic alkyl group (also: cycloalkyl group) understood.
  • Preferred linear or branched (C 1 -C 6) -alkyl groups are selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl.
  • Preferred branched (C3-Cio) -alkyl groups are selected from iso-propyl, sec-butyl, isobutyl, tert-butyl, neo-pentyl, iso-octyl, 2-ethylhexyl, 2-ethylheptyl.
  • Preferred cyclic alkyl groups ((C3-C6) -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, in particular acetyl.
  • Preferred (C 2 -C 6) -acyloxy groups are selected from acetyloxy, propanoyloxy, butanoyloxy, pentanoyloxy and hexanoyloxy, especially acetyloxy.
  • an alkoxy group is understood as meaning an alkyl group which bonds via an oxygen atom and is selected from a linear alkyl group of branched alkyl group or cyclic alkyl group (also: cycloalkyl group).
  • Preferred (C 1 -C 6) -alkoxy groups are
  • Preferred (C 2 -C 6) -acylamino groups are acetylamino, propanoylamino, butanoylamino, pentanoylamino and hexanoylamino, in particular acetylamino.
  • Preferred aryl groups are phenyl, naphthyl, anthracenyl, these being substituted or unsubstituted.
  • Aroyl groups are arene carbonyl groups in which a carbonyl group bonds directly to the aromatic ring system.
  • Preferred aroyl groups are benzoyl, naphthoyl and anthracenoyl, which are substituted or unsubstituted.
  • Aroyloxy groups are aroyl groups that attach via an additional carbon atom-binding oxygen atom.
  • Preferred aroyloxy groups are selected from benzoyloxy, naphthoyloxy and anthracenoyloxy, these being substituted or unsubstituted.
  • a preferred aryloxy group is the phenoxy group or the naphthoxy group, which are substituted or unsubstituted.
  • Preferred aryl- (C 1 -C 3) -alkyl groups are selected from benzyl, 2-phenylethyl, naphthylmethyl,
  • 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-yl-ethyl, indole
  • the viscoelastic, solid-form surfactant compositions according to the invention comprise at least one 2,5-diketopiperazine compound of the formula (I) in which R 5 represents a (Ci-C 4 ) -hydrocarbyl group substituted by an aromatic radical in particular a radical of the following formulas (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 of the 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 turn out to be particularly preferred when the compositions of the invention (in each case based on the total weight of
  • composition 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.55 wt.%, In particular of at least 0.7 wt .-%, particularly preferably of at least 0.8 wt .-%. More preferred (in each case based on the total weight of the composition) 2,5-diketopiperazine compound according to formula (I) in a total amount of 0.5 to 3.0 wt.%, In particular from 0.7 to 2.5 wt. %, most preferably from 0.8 to 2.0 wt%, most preferably from 0.85 to 1.5 wt%.
  • compositions according to the invention comprise at least one 2,5-diketopiperazine compound of the formula (Ia)
  • R 1 and R 5 are as defined under formula (I) (vide supra).
  • R 1 and R 5 are as previously defined under formula (I) (vide supra).
  • the numerals 3 and 6 positioned on the ring atoms in formula (lb) are illustrative only of positions 3 and 6 of the diketopiperazine ring, as generally used in the context of the invention for the
  • Particularly preferred compounds of the formula (I-b) have the following radicals:
  • 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 are necessarily a hydrogen atom.
  • At least one compound of the formula (I) is contained, 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, hydroxy, methyl, ethyl, isopropyl, n-propyl, n-butyl 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, hydroxy, methyl, ethyl, isopropyl, n-propyl, n-butyl C 2 -C 6) acyloxy group, an aryloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.
  • compositions according to the invention which have been found to contain at least one compound according to formula (I) in which R 5 is a hydrogen atom, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a 2- (Methylsulfanyl) ethyl group, a hydroxymethyl group, a (C1-C3) alkoxymethyl group, a benzyloxymethyl group, an acetyloxymethyl group, a
  • Benzoyloxymethyl group a tosyloxymethyl group, a 1-hydroxyethyl group, a 1- (C 1 -C 3) alkoxy) ethyl group, a 1- (acetyloxy) ethyl group, a 1- (benzoyloxy) ethyl group, a 1- (tosyloxy) ethyl group, a mercaptomethyl group , a (C 1 -C 3) -alkylsulfanylmethyl group, an acetylsulfanylmethyl group, a benzoylsulfanylmethyl group, a tosylsulfanylmethyl group, a group according to formula (II),
  • R ' is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 2 to C 4 ) -alkenyl group, an aryl group or an aryl- (C 1 to C 4 ) -alkyl group,
  • R ' is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 2 to C 4 ) -alkenyl group, an aryl group or an aryl- (C 1 to C 4 ) -alkyl group,
  • n 0 or 1
  • X is an oxygen atom or a group -NH- and R "is a hydrogen atom, a (Ci-C 4 ) alkyl group, a (C2 to C 4 ) alkenyl group, an aryl group or a Aryl- (C 1 to C 4 ) -alkyl group,
  • n 1 or 2 and R "and R"'independently of one another represent a hydrogen atom, a (C 1 -C 4 ) -alkyl group, a (C 2 -C 6) -acyl group, a benzoyl group, an aryl- (C 1 to C 4 ) - alkyl group, an aminoiminomethyl group or a tosyl group,
  • n is 0 or 1 and R is a hydrogen atom, a hydroxy group, a (C 1 -C 4 ) -alkyl group, a (C 1 -C 4 ) -alkoxy group, an N- (C 1 -C 4 ) -alkylamino group, an aryl group (Ci to C4) - alkyl group, an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group.
  • R 'represented by formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group.
  • R 'represented by the formula (III) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group.
  • R 'represented by the formula (IV) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group.
  • R "and R” 'according to formula (V) are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, benzyl, benzoyl, acetyl, one
  • R of the formula (VI) is a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, a phenyl group, a methoxy group, an acetyloxy group, a
  • Tosyloxy a triflyloxy group, a benzyloxy group or a benzoyloxy group.
  • 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 exemplified in formula (l-b).
  • the 2,5-diketopiperazine compound of the formula (I) of the inventive compositions is preferably based on the stereochemistry of the carbon atoms at 3- and 6-position of the 2,5-Diketopiperazinringes the configuration isomer 3S, 6S, 3R, 6S, 3S, 6R , 3R, 6R or mixtures thereof, more 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-isopropyl-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, 3-benzyl-6- (4-imi
  • the viscoelastic, solid-shaped ones of the invention contain
  • compositions preferably 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-carboxymethyl-piperazine-2,5-dione, or mixtures thereof.
  • compounds with the aforementioned configuration isomers are preferably suitable for selection, the S, S configuration being particularly preferred in each case.
  • (3S, 6S) -3,6-bis (4-hydroxybenzyl) -piperazine-2,5-dione is again most preferred.
  • the 2,5-diketopiperazine compounds present in the agents according to the invention are prepared by means of known synthesis methods (compare Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237).
  • the viscoelastic solid surfactant composition of the present invention contains water. It is preferred if in the surfactant composition water, based on the total weight of the composition, preferably in a total amount of between 0 and 70 wt .-%, more preferably between 4 and 70 wt .-%, more preferably between 10 and 70 wt .-%, more preferably between 0 and 60 wt .-%, more preferably between 4 and 60 wt .-%, more preferably between 10 and 60 wt .-%, more preferably between 0 to 40 wt .-%, more preferably between 4 and 40 wt .-%, more preferably between 10 and 40 wt .-%, particularly preferably between 0 to 25 wt .-%, more preferably between 4 and 25 wt .-%, more preferably between 10 and 25 wt .-%, is contained.
  • the proportion of water in the surfactant composition is most preferably 20% by weight or less, again more preferably 15% by weight or less, again more preferably 12% by weight or less, especially 4 to 20% by weight.
  • the percentages by weight are based on the total weight of the composition.
  • the surfactant composition additionally contains at least one organic radical, as well as its stability is improved, if preferably the surfactant composition additionally contains at least one organic radical, as well as its stability is improved, if preferably the surfactant composition additionally contains at least one organic radical, as well as its stability is improved, if preferably the surfactant composition additionally contains at least one organic radical, as well as its stability is improved, if preferably the surfactant composition additionally contains at least one organic
  • Solvents having at least one hydroxyl group, no amino group and one
  • Said organic solvent is again preferably selected from (C 2 -C 5) -alkanols having at least one hydroxyl group (particularly preferably selected from the group consisting of ethanol, ethylene glycol, 1,2-propanediol, glycerol, 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 molecular weight M w of at most 500 g / mol, glycerol 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
  • Surfactant composition is preferably additionally at least one polyalkylene oxide compound having a weight-average molecular weight 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.
  • polyalkylene oxide compound polyethylene oxide having a weight average molecular weight M w of at least 4000 g / mol, in particular of at least 6000 g / mol, more preferably of at least 8000 g / mol.
  • the stability of said surfactant composition is further improved if the surfactant composition additionally comprises at least one polymeric polyol, in particular
  • Polyvinyl alcohol is included.
  • Polymeric polyols have more than 3 hydroxy groups according to the present invention.
  • suitable polymeric polyols preferably have an average molecular weight of 4000 to 100000 g / mol.
  • the surfactant composition according to the invention preferably contains, based on the total weight thereof, a total amount of from 1 to 30% by weight, in particular from 2 to 20% by weight, of the polymeric polyol.
  • Polyvinyl alcohols are thermoplastics which are produced as a white to yellowish powder mostly by hydrolysis of polyvinyl acetate.
  • Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Preference is given to polyvinyl alcohols having an average molar mass of 30,000 to 60,000 g / mol.
  • 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 especially 82 to 88 mol%. % is.
  • the water-soluble packaging is at least 20 wt .-%, particularly preferably at least 40 wt .-%, most preferably to at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%, is.
  • PVOH powders having the aforementioned 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. Particularly suitable are the Poval® qualities, in particular the grades 3-83, 3-88 and 3-98 and Mowiol® 4-88 from Kuraray.
  • the water solubility of polyvinyl alcohol can be improved by post-treatment with aldehydes
  • ketones are changed.
  • polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.
  • the reaction products of polyvinyl alcohol and starch are particularly advantageous.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • PVOH and / or gelatin are particularly suitable for producing surfactant compositions which meet the requirements shown above.
  • a surfactant composition according to the invention which comprises PVOH and at least one organic solvent as described above is particularly preferred.
  • the composition additionally contains at least one stabilizer selected from magnesium oxide, inorganic salt of Mg, Ca, Zn, Na or K (especially sulfate, carbonate or acetate, more preferably magnesium sulfate, zinc acetate or calcium acetate), acetamido 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 (especially sulfate, carbonate or acetate, more preferably magnesium sulfate, zinc acetate or calcium acetate), acetamido monoethanolamine, hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof.
  • Surfactant composition to increase product safety at least one bittering agent is included.
  • Preferred bittering agents have a bitter value of at least 1,000, preferably at least 10,000, more preferably at least 200,000.
  • the standardized method described in the European Pharmacopoeia 5th Edition, Grundwerk, Stuttgart 2005, Volume 1 General Part Monograph Groups, 2.8.15 Bitter Value, p. 278) is used to determine the bitterness value.
  • As a comparison serves an aqueous solution of quinine hydrochloride whose bitterness value is set at 200,000. This means that 1 gram of quinine hydrochloride makes 200 liters of water bitter.
  • the interindividual taste differences in the organoleptic test of bitterness are compensated by a correction factor in this method.
  • Very particularly preferred bittering agents are selected from denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof, more preferably
  • Glycosides are organic compounds of the general structure R-O-Z, in which an alcohol (R-OH) is connected via a glycosidic bond with a sugar moiety (Z).
  • Suitable glycosides are, for example, flavonoids such as quercetin or naringin or
  • Iridoid qlvcosides such as aucubin and especially seccoidoid qlvcosides such as amarogentin,
  • Isoprenoids are compounds that formally derive from isoprene. Examples are in particular terpenes and terpenoids.
  • Suitable isoprenoids include, for example, sequiterpene lactones, such as absinthine, artabsine, cnicin, lactucin, lactucopyrin or salzolidideolide, monoterpene ketones (thujones), such as
  • ⁇ -thujone or ⁇ -thujone tetranortriterpenes (limonoids) such as desoxylimones, deoxylmonic acid, limonin, ichangin, isobaconic acid, obacunone, obacunonic acid, nomilin or nomilinic acid, terpenes such as marrubin, premarubin, carnosol, carnosic acid or quassin.
  • limonoids such as desoxylimones, deoxylmonic acid, limonin, ichangin, isobaconic acid, obacunone, obacunonic acid, nomilin or nomilinic acid, terpenes such as marrubin, premarubin, carnosol, carnosic acid or quassin.
  • Alkaloids refer to naturally occurring, chemically heterogeneous, mostly alkaline, nitrogen-containing organic compounds of secondary metabolism which act on the animal or human organism.
  • Suitable alkaloids are, for example, quinine hydrochloride, quinine hydrogen sulfate,
  • Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.
  • Denatonium benzoate (eg available as Bitrex ®).
  • the viscoelastic, solid surfactant composition contains based on the
  • Total weight preferred bittering agent 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), more preferably of at most 1: 500, most preferably of at most 1: 1000.
  • the viscoelastic solid surfactant composition can be prepared by first placing a liquid composition containing the organic compound of component (ii) at a temperature above the sol-gel transition temperature of the liquid composition and then forming the heated liquid composition into a mold , preferably in a cavity of a trough mold, and cooled in said form below the sol-gel transition temperature to form a viscoelastic, solid shaped body.
  • the particular liquid composition is in the form of curing the liquid
  • composition brought under the sol-gel transition temperature of the liquid composition It is inventively preferred when the liquid composition for forming said shaped body to not less than 20 ° C, in particular not less than 25 ° C, more preferably not less than 30 ° C, cooled.
  • the sol-gel temperature can be determined by conventional methods. As part of the analysis
  • 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 to determine the sol-gel temperature until the organic compound of
  • Component (ii) has completely dissolved and it creates a transparent solution.
  • This solution is cooled in the heating thermoshaker to 80 ° C with 0 rpm.
  • a temperature-dependent oscillating measurement (devices as above (vide supra)) at a deformation of 0.1%, a frequency of 1 Hz and cooling rate of 5 ° C / min is performed.
  • the temperature is given as 80 ° C and the Shut down the top plate to minimize the temperature difference between the bottom and top plates.
  • the top plate is raised and 0.5 g of the sample is carefully applied to the bottom plate with a pipette as a sol. Then the upper plate is shut down and the measurement is started. The measurements are carried out at different temperatures.
  • a corresponding shaped article can also be produced by extrusion of the viscoelastic, solid-form surfactant composition, with optional subsequent rounding. This can produce a free-flowing product or pellets.
  • the viscoelastic, solid-form surfactant composition of the first subject of the invention is present as a shaped article.
  • a molded body is a single body that stabilizes itself in its embossed form.
  • This dimensionally stable body is formed from a molding compound (e.g., a composition) by deliberately placing this molding material in a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.
  • a molding compound e.g., a composition
  • All possible shapes are possible, such as sphere, cube, cuboid, round disc, tub, shell, prism, octahedron, tetrahedron, egg shape, dog, cat, mouse, horse, torso, bust, cushion, automobile, oval disc with imprinted trademark, and much more.
  • the shaped body of the viscoelastic, solid-form surfactant composition of the first subject 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 shaped body of the viscoelastic, solid-form surfactant composition of the first subject of the invention has a weight of at most 80 g, in particular of at most 70 g, more preferably of at most 50 g, very particularly preferably of at most 40 g, most preferably of at most 30 g, owns.
  • the aforementioned minimum weights of the molding are particularly preferred.
  • Surfactant composition of the first subject of the invention has a weight of from 10 to 80 g, in particular from 10 to 70 g, more preferably from 10 to 50 g, most preferably from 10 to 30 g, for example 15 g or 25 g. It is again preferred if said
  • Molded body contains surfactant in the total amounts marked as preferred (vide supra).
  • the shaped body of said viscoelastic solid composition may also comprise at least two different viscoelastic, solid surfactant compositions of the first Subject of the invention to form at least two phases, preferably of at least two different colored phases included.
  • a mold body can be prepared as a first phase, in the well a second viscoelastic, solid-form surfactant composition of the first subject of the invention is introduced as the second phase.
  • the shaped body may be formed of various, viscoelastic, solid compositions arranged as stacked phases.
  • a corresponding molded body of the surfactant composition according to the invention may preferably be used as a container with at least one well, e.g. in the form of a tub or shell, be designed such that the volume of the walls is smaller than the total volume of all troughs.
  • the walls of a molded body of this embodiment preferably have an average thickness of not more than 5 mm, in particular not more than 2 mm, more preferably not more than 1 mm.
  • the total volume of the wells of this embodiment preferably has a volume of at least 5 ml, more preferably 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.
  • a phase differs from another phase by various features, for example, ingredients, external appearance, etc.
  • different phases can be visually distinguished.
  • a first phase is clearly differentiated from a second phase.
  • these can preferably likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color.
  • a visual differentiation of the phases for example due to a color or transparency difference is preferably possible.
  • Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye.
  • the individual phases may have different properties when used.
  • At least one bittering agent has been incorporated homogeneously into the shaped body and / or the surface of the shaped body has been provided by coating with at least one bittering agent. It is preferred to incorporate the at least one bittering agent homogeneously into the shaped body as an ingredient of the viscoelastic, solid surfactant composition.
  • Preferred bittering agents and amounts are the aforementioned (vide supra).
  • Preferred powdering agents are selected from talc, sodium sulfate, starch, pectin, amylopectin, dextrin, lactic acid, lactose or mixtures thereof.
  • the surfaces of the molded article may be printed for further aesthetic enrichment and / or for attachment of clues or manufacturer names.
  • the use of inkjet printing is preferred.
  • compositions are also for providing a composition of the invention.
  • Shaped body preferred.
  • a second object of the invention is a portion containing at least one viscoelastic solid surfactant composition of the first subject of the invention.
  • the portion contains the viscoelastic, solid-form surfactant composition according to the invention of the first subject of the invention as a shaped body.
  • the portion based on its total weight, the molding to at least 5 wt .-%, in particular at least 15 wt .-%, in particular at least 50 wt .-%, in particular at least 80 wt .-% , in particular at least 90 wt .-%, particularly preferably at least 95 wt .-%, contains.
  • One serving is a standalone dosing unit that provides a quantity of fabric treatment agent for one application, preferably for use in a washing machine.
  • the viscoelastic, solid surfactant composition of the present invention may be either the sole textile treatment agent of the portion, or may be formulated in portion with at least one additional composition other than the viscoelastic solid surfactant composition of the first subject of the invention, and in total form the textile treatment agent of the portion.
  • the portion according to the invention comprises at least one shaped body of the viscoelastic, solid-form surfactant composition of the first
  • Invention article which has a weight of at least 1 g, preferably of at least 5 g, more preferably of at least 10 g possesses.
  • the portion according to the invention comprises at least one shaped body of the viscoelastic, solid-form surfactant composition of the first
  • Invention article which has a weight of at most 80 g, in particular of at most 70 g, more preferably of at most 50 g, most preferably of has at most 40 g.
  • the aforementioned minimum weights of the molding are particularly preferred.
  • the portion according to the invention very particularly preferably has a shaped body of the viscoelastic, solid-form surfactant composition of the first subject of the invention with a weight of from 1 to 80 g, in particular from 1 to 70 g, more preferably from 1 to 50 g, more preferably from 1 to 30 g, in particular from 10 to 80 g, especially from 10 to 70 g, more preferably from 10 to 50 g, most preferably from 10 to 30 g, for example 15 g or 25 g.
  • said shaped body contains surfactant in the total amounts characterized as being preferred (vide supra).
  • (P1) Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition of the first subject of the invention, the shaped body having a weight of at least 1 g, preferably of at least 5 g, more preferably at least 10 g, most preferably from 10 to 30 g.
  • (P2) Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition of the first subject of the invention, the shaped body being transparent and having a weight of at least 1 g, preferably of at least 5 g, more preferably at least 10 g, most preferably from 10 to 30 g.
  • anionic surfactant 10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant preferably at least one C9-i3-alkylbenzenesulfonate is contained, and
  • nonionic surfactant preferably at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included, with the proviso that surfactant in a Total amount of from 10 to 70% by weight, in particular from 15 to 70% by weight,
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a
  • 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- C3) alkyl group, a heteroaryl group, a hetroaryl (Ci-C3) alkyl group, a (Ci-C4) hydroxyalkyl group, a (C1-C4) -aminoalkyl group, a carboxy (Ci-C3) alkyl group, wherein at least two of the radicals R 1 to R 4 together with the remainder of the molecule can form a 5 or 6-membered ring,
  • R 5 represents a hydrogen atom, a linear (C 1 to C 6) alkyl group, a branched (C 3 to Cio) alkyl group, a (C 3 to C 6) cycloalkyl group, a (C 2 to C 6) alkenyl group, a (C 2 -C 6) alkynyl group, a (C 1 -C 4) -hydroxyalkyl group, a (C 1 -C 4) -alkoxy (C 1 -C 4) -alkyl group, a (C 1 -C 4) -acyloxy- (C 1 -C 4) -alkyl group, a Aryloxy- (C 1 -C 4) -alkyl group, a 0- (aryl- (C 1 -C 4) -alkyl) oxy- (C 1 -C 4) -alkyl group, a (C 1 -C 4) -alkylsulfanyl- (C 1
  • (P4) Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition, based on the total weight of the
  • nonionic surfactant 2 to 35 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant preferably at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included, with the proviso that surfactant in a Total amount of 10 to 70 wt .-% is included, and
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a
  • the shaped body is preferably coated with water-soluble material.
  • a coating has also proved to be favorable with regard to the storage stability of the shaped bodies according to the invention used in the portions.
  • said shaped 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 effected for example by spraying a solution or by immersion in a melt, wherein in the latter method, the melting temperature is preferably below the sol-gel temperature. It may again be preferred to spray the shaped bodies coated with at least one water-soluble material with at least one pulverulent solid.
  • Preferred means for Abpud réelle are the aforementioned (vide supra).
  • a portion according to the invention may comprise at least one chamber with walls of water-soluble material into which at least one shaped body of a viscoelastic, solid-form surfactant composition of the first subject of the invention is introduced. Summed up over all chambers of the portion, the compositions made up in total yield the portion of the portion to be dosed (here a textile treatment agent).
  • a textile treatment agent a viscoelastic, solid-form surfactant composition of the first subject of the invention
  • a chamber is a space bounded by walls (e.g., by a foil), which may exist even without the material to be dosed (possibly changing its shape).
  • a layer of a surface coating thus does not explicitly fall under the definition of a wall.
  • the water-soluble material in a pouch forms the walls of the chamber and thereby envelops the compositions of the fabric treatment agent.
  • Soluble in water is a material, when at 20 ° C 0.1 g of the material with stirring
  • the water-solubility of the film-forming material used for the production of pouches can be determined by means of a square film of said material (film: 22 x 22 mm with a thickness of 20 mm) fixed in a square frame (inside edge length: 20 mm) 76 pm) according to the following measurement protocol.
  • Said framed film is immersed in 800 mL of distilled water heated to 20 ° C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, 1000 mL beaker, low mold) so that the surface of the clamped film is at right angles to the Bottom surface of the beaker is arranged, 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 such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom.
  • the material should dissolve with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm) within 600 seconds in such a way that with the naked eye, no single solid-shaped film particles are more visible.
  • the water-soluble material generally used for coating the shaped body preferably contains at least one water-soluble polymer. It is particularly preferable that the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble material and water-soluble films as the water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol 1 , more preferably 30,000 to 100,000 gmol 1 and especially from 40,000 to 80,000 gmol -1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers.
  • 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
  • polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added to the water-soluble material.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates 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 from 75 to 120 ⁇ m.
  • a bittering agent is selected from the aforementioned bittering agents (vide supra), in particular denatonium benzoate.
  • Portions of the present invention in the form of a pouch can be made by either vertical fill seal (VFFS) or thermoforming techniques.
  • walls of at least one chamber are produced by sealing at least one film of water-soluble material, in particular by sealing in the context of a form-fill-seal method.
  • the thermoforming process generally includes forming a first layer of water-soluble film material to form at least one protrusion for receiving at least one composition therein, filling the composition into the respective protrusion, covering the composition-filled protrusions with a second layer of water-soluble one Film material and sealing the first and second layers together at least around the protrusions.
  • Another object of the invention is a method for substrate treatment comprising the method steps
  • Viscoelastic, solid-form surfactant composition containing based on the
  • composition according to item 1 characterized in that the
  • Tenside 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 (at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz) and the memory module in the frequency range between 10 3 Hz and 10 2 is at least twice greater than the loss modulus, preferably at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus.
  • Composition according to item 1 or 2 characterized in that it contains at least one anionic surfactant.
  • Composition according to item 3 characterized in that at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates,
  • Olefinsulfonates C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
  • Composition according to point 1 to 4 characterized in that as surfactant at least one compound of formula (T-1) is contained,
  • R 2 is a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical,
  • XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO)
  • composition according to one of the items 1 to 7 characterized in that it has a total surfactant content of 10 to 60 wt .-%, in particular from 15 to 65 wt .-%, preferably from 20 to 60 wt .-%, based on their total weight ,
  • Composition according to one of the items 1 to 8 characterized in that the further cyclic structural unit c) is selected from at least one 2,5-diketopiperazine structural unit.
  • Composition according to one of the items 1 to 9 characterized in that the carbocyclic structural unit b) is selected from at least one phenyl group.
  • Composition according to one of the items 1 to 10 characterized in that the component (ii) is selected from at least one diketopiperazine compound of the formula (I)
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a
  • R 5 represents a hydrogen atom, a linear (C 1 to C 6) alkyl group, a branched (C 3 to Cio) alkyl group, a (C 3 to C 6) cycloalkyl group, a (C 2 to C 6) alkenyl group, a (C 2 -C 6) alkynyl group, a (C 1 -C 4) -hydroxyalkyl group, a (C 1 -C 4) -alkoxy (C 1 -C 4) -alkyl group, a (C 1 -C 4) -acyloxy- (C 1 -C 4) -alkyl group, a Aryloxy- (C 1 -C 4) -alkyl group, a 0- (aryl- (C 1 -C 4) -alkyl) oxy- (C 1 -C 4) -alkyl group, a (C 1 -C 4) -alkylsulfanyl- (C 1
  • composition according to item 1 characterized in that according to formula (I) R 1 binds in the para position of the phenyl ring and preferably R 2 to R 4 are hydrogen.
  • Hydrogen atom hydroxy group, methyl group, ethyl group, iso-propyl group, n-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, phenyl group, benzyl group, etc.
  • 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.
  • R ' is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 2 to C 4 ) -alkenyl group, an aryl group or an aryl- (C 1 to C 4 ) -alkyl group,
  • R ' is a hydrogen atom, a (C 1 to C 4 ) -alkyl group, a (C 2 to C 4 ) -alkenyl group, an aryl group or an aryl- (C 1 to C 4 ) -alkyl group,
  • n 0 or 1
  • X is an oxygen atom or a group -NH- and R "is a hydrogen atom, a (Ci-C 4 ) alkyl group, a (C2 to C 4 ) alkenyl group, an aryl group or a Aryl- (C 1 to C 4 ) -alkyl group,
  • n 1 or 2 and R "and R"'independently of one another represent a hydrogen atom, a (C 1 -C 4 ) -alkyl group, a (C 2 -C 6) -acyl group, a benzoyl group, an aryl- (C 1 to C 4 ) alkyl group, an aminoiminomethyl group or a tosyl group,
  • n is 0 or 1 and R is a hydrogen atom, a hydroxy group, a (C 1 -C 4 ) -alkyl group, a (C 1 -C 4 ) -alkoxy group, an N- (C 1 -C 4 ) -alkylamino group, an aryl group (C 1 to C 4 ) alkyl group, an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group.
  • composition according to item 14 characterized in that R 'according to formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group.
  • R ' according to formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group.
  • R ' represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl 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 iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group.
  • R according to formula (VI) is a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl 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.
  • composition according to one of the items 1 to 20, characterized in that the organic compound of component (ii) is selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5- diketopiperazine, 3-benzyl-6- (4-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
  • composition according to one of the preceding points, characterized in that it additionally contains at least one organic solvent having at least one hydroxyl group, no amino group and having a molecular weight of at most 500 g / mol (preferably selected from (C2-Cs) -alkanols having at least one hydroxyl group
  • composition according to item 23 characterized in that said organic solvent is contained in a total amount of from 5 to 40% by weight, in particular from 10 to 35% by weight.
  • Composition according to one of the preceding points characterized in that in addition at least one polyalkylene oxide compound having a weight average molecular weight M w of at least 4000 g / mol is contained.
  • Composition according to item 25 characterized in that
  • Polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof.
  • Composition according to one of the preceding points characterized in that additionally at least one polymeric polyol, in particular polyvinyl alcohol, is contained.
  • Composition according to one of the preceding points characterized in that the storage modulus is in a range from 10 5 Pa to 10 7 Pa.
  • composition according to one of the preceding points characterized in that it is in the form of a shaped body, in particular having a weight of at least 1 g, preferably of at least 5 g, more preferably of 10 to 30 g.
  • Composition according to one of the preceding points characterized in that the composition is transparent.
  • Portion according to item 32 characterized in that it additionally comprises at least one further composition.
  • Portion according to one of the items 32 or 33 characterized in that it is designed as a shaped body of at least one surfactant composition of points 1 to 23, wherein the shaped body preferably has a weight of at least 1 g, more preferably of at least 5 g, most preferably of 10 up to 30 g.
  • Portion according to item 32 or 33 characterized in that it comprises at least one chamber with wall of water-soluble material, wherein the portion contains at least one viscoelastic, solid shaped article according to item 22.
  • endocyclic double bonds in particular at least one carbocyclic, aromatic structural unit,
  • composition is then brought, and then the heated liquid composition in a mold, preferably in a cavity of a trough mold, given and cooled in said mold below the sol-gel transition temperature to form a viscoelastic, solid shaped body.
  • IR spectra were measured on a Nicolet Thermo iS10 scientific spectrometer with diamond ATR unit. The absorption bands were reported in cnr 1 with the following relative intensity data: 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 down to 0 ° C. TFA (5.0 eq) was added in one portion and stirred until the starting material had reacted. Meanwhile, the reaction mixture was slowly warmed to 25 ° C. All fleeting
  • 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 NEt3 (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 (3c) and dried in a fine vacuum. Finally, the cyclized dipeptide was obtained as a colorless solid.
  • 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 until complete conversion at 25 ° C. After filtration and removal of the solvent under reduced pressure, the deprotected cyclic dipeptide was isolated as a colorless solid.
  • IR (ATR, neat): v 3184 (w), 3033 (w), 2979 (w), 2889 (w), 1663 (s), 1484 (m), 1466 (s), 1455 (s), 1371 (w), 1338 (s), 1242 (w), 121 1 (w), 1 191 (w), 1 160 (w), 1 104 (m), 1054 (m), 969 (w), 923 ( w), 856 (s),
  • IR (ATR, neat): v 3535 (w), 3204 (br), 3029 (w), 1653 (s), 1615 (m), 1589 (m), 1516 (s), 1496 (w), 1464 (s), 1331 (m), 1274 (m), 1248 (m), 1224 (m), 1200 (m), 1173 (s), 1101 (m), 1078 (m), 1013 (w), 878 (w), 805 (s), 750 (s), 696 (s), 660 (s) cm -1 .
  • IR (ATR, neat): v 3190 (w), 3060 (w), 2969 (w), 2902 (w), 1732 (m), 1672 (s), 1456 (m), 1436 (m), 1394 (w), 1338 (m), 1260 (m), 1215 (w), 1152 (s), 1102 (m), 1012 (w), 956 (m), 864 (m), 844 (m), 819 (m), 753 (s), 700 (s), 656 (m) cm 1 .
  • IR (ATR, neat): v 3179 (w), 3030 (w), 2881 (w), 2852 (w), 1660 (s), 161 1 (m), 1508 (s), 1463 (s), 1453 (s), 1376 (w), 1340 (m), 1310 (m), 1297 (m), 1237 (s), 1225 (s), 1 174 (s), 1 1 10 (m), 1042 ( m), 1016 (m), 922 (m), 833 (s), 808 (s), 773 (s), 755 (m), 732 (s), 721 (s), 694 (s), 653 ( m) cm 1 .
  • IR (ATR, neat): v 3516 (w), 3145 (w), 1665 (s), 1614 (m), 1598 (m), 1515 (s), 1456 (s), 1378 (w), 1337 (m), 1308 (w), 1272 (m), 1237 (s), 1 173 (m), 1 104 (m), 1085 (w), 1013 (w), 950 (w), 925 (w) , 884 (w), 825 (s), 796 (s), 776 (s), 717 (m) cm 1 .
  • compositions E1 to E5 according to the invention (compare Table 2.2 in conjunction with Table 2.1) were prepared.
  • Active substance by weight of the selected composition from Table 2.1
  • the clear, liquid detergents F1 to F6 were prepared according to Table 3.1.
  • a premix was used as a solution of 1.0 g of (3S, 6S) -3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine (DKP 10) and 92 g of the selected liquid detergent of Table 3.1 prepared under heating. 15 g of the still hot and clear premix were incorporated into 85 g of the room temperature liquid detergent of Table 3.1 with vigorous stirring. 19 g of the resulting solution was quickly added to a cube-well mold. The temperature of the solution was gradually lowered to room temperature in the well. After solidification, the molded body was removed from the trough.
  • liquid dishwashing detergents G1 and G2 were prepared according to Table 4.1.
  • a premix was first prepared from the liquid dishwashing detergent G1 of Table 4.1 as a solution of 1.0 g of (3S, 6S) -3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine (DKP 10) and 92 g G1 of Table 4.1 prepared under heating. 15 g of the still hot and clear premix was in 85 g of the room temperature
  • Dishwashing agent G1 of Table 4.1 incorporated with vigorous stirring. 19 g of the resulting solution was quickly added to a cube-well mold. The temperature of the solution was gradually lowered to room temperature in the well. After solidification, the molded body was removed from the trough.
  • a first premix was first prepared from a liquid dishwashing detergent G2 (phase 1) of 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 of G2 (phase 1) of Table 4.1 prepared under heating.
  • a second premix of composition G2 (phase 2) of Table 4.1 was prepared analogously.
  • phase 1 After solidification, the molded body of phase 1 was left in the trough. 15 g of the still hot and clear premix 2 were dissolved in 85 g of room temperature
  • Dishwashing agent G2 (phase 2) of Table 4.1 incorporated with vigorous stirring. 9.5 g of the resulting solution was rapidly added to the cube-well mold on the already cured G2 shaped body (Phase 1). The temperature of the solution was gradually lowered to room temperature in the well.
  • the resulting G2 shaped body was removed from the trough after phase 2 hardening.
  • a stable one-piece molded article with two phases (red and blue) was obtained.

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne une composition tensioactive viscoélastique solide pour le traitement des textiles, contenant, rapporté à son poids total, (i) une quantité totale de 0,1 à 70 % en poids d'au moins un tensioactif et (ii) au moins un composé organique ayant un poids moléculaire de < 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 ayant au moins deux liaisons doubles endocycliques, en particulier au moins un motif constitutif aromatique carbocyclique et c) au moins un autre motif constitutif cyclique présentant au moins deux groupes carbonyle et (iii) de l'eau. La composition tensioactive présente une forme bien soluble, esthétiquement attrayante et stable au stockage d'une composition solide pour préparer des bains tensioactifs.
EP19702201.5A 2018-02-06 2019-01-21 Composition tensioactive viscoélastique solide Pending EP3749738A1 (fr)

Applications Claiming Priority (2)

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DE102018201830.8A DE102018201830A1 (de) 2018-02-06 2018-02-06 Viskoelastische, festförmige Tensidzusammensetzung
PCT/EP2019/051336 WO2019154612A1 (fr) 2018-02-06 2019-01-21 Composition tensioactive viscoélastique solide

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Publication number Priority date Publication date Assignee Title
DE102018209002A1 (de) 2018-06-07 2019-12-12 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Fließgrenze
ES2944450T3 (es) * 2019-08-21 2023-06-21 Unilever Ip Holdings B V Composición sólida detergente

Family Cites Families (18)

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Publication number Priority date Publication date Assignee Title
US4116885A (en) 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
CA1190695A (fr) 1981-05-14 1985-07-16 George J. Stockburger Agent anionique pour le traitement des textiles
DE3324258A1 (de) 1982-07-09 1984-01-12 Colgate-Palmolive Co., 10022 New York, N.Y. Nichtionogene waschmittelzusammensetzung mit verbesserter schmutzauswaschbarkeit
EP0185427B1 (fr) 1984-12-21 1992-03-04 The Procter & Gamble Company Polyesters blocs et composés similaires utiles comme agents de détachage dans les compositions de détergent
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
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
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
ATE134669T1 (de) 1988-08-26 1996-03-15 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
WO2002086074A2 (fr) 2001-04-20 2002-10-31 Regents Of The University Of Minnesota Compositions permettant la delivrance de composes dans des cellules et procedes d'utilisation
DE102008051799A1 (de) 2008-10-17 2010-04-22 Henkel Ag & Co. Kgaa Stabilisierung von Mikrokapsel-Slurries
AR080507A1 (es) * 2010-03-12 2012-04-11 Procter & Gamble Composiciones detergentes liquidas que comprenden un gelificante diamido y los procesos para elaborarlas
DE102012214607A1 (de) 2012-08-16 2014-02-20 Henkel Ag & Co. Kgaa Wasserlösliche Verpackung mit Bittermittel I
DE102012214608A1 (de) 2012-08-16 2014-02-20 Henkel Ag & Co. Kgaa Wasserlösliche Verpackung mit Bittermittel II
EP3060193B1 (fr) * 2013-10-25 2017-07-05 Unilever Plc. Bâtons antiperspirants sous forme d'émulsion

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DE102018201830A1 (de) 2019-08-08

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