EP3638756A1 - Composition tensioactive viscoélastique, solide, présentant une teneur élevée en tensioactif - Google Patents

Composition tensioactive viscoélastique, solide, présentant une teneur élevée en tensioactif

Info

Publication number
EP3638756A1
EP3638756A1 EP18732005.6A EP18732005A EP3638756A1 EP 3638756 A1 EP3638756 A1 EP 3638756A1 EP 18732005 A EP18732005 A EP 18732005A EP 3638756 A1 EP3638756 A1 EP 3638756A1
Authority
EP
European Patent Office
Prior art keywords
group
surfactant
weight
composition according
composition
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
EP18732005.6A
Other languages
German (de)
English (en)
Inventor
Peter Schmiedel
Filiz Yapici
Boray TORUN
Anna KLEMMER
Michael Dreja
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
Priority claimed from DE102017210141.5A external-priority patent/DE102017210141A1/de
Priority claimed from DE102017210143.1A external-priority patent/DE102017210143A1/de
Priority claimed from DE102017223456.3A external-priority patent/DE102017223456A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3638756A1 publication Critical patent/EP3638756A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/26—Sulfonic acids or sulfuric acid esters; Salts thereof derived from heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • Surfactant compositions for providing surfactant-containing liquors for textile treatment, in particular for cleaning textiles are provided.
  • Textile treatment agents are usually in solid form (for example as a powder or tablets) or in liquid form (or else as a flowing gel).
  • liquid detergents or cleaners are becoming increasingly popular with consumers.
  • Solid textile treatment agents have the advantage that, in contrast to liquid textile treatment agents, they do not require any preservatives and the ingredients contained therein (such as, for example, bleaches or enzymes) can be incorporated more stably.
  • 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 increasingly 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
  • Shaped bodies to provide that dissolve well in contact with water in water or can be dispersed therein.
  • 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.
  • An object of the invention is therefore as a first embodiment a viscoelastic, solid surfactant composition for textile treatment, containing based on their total weight
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • R, R 2 and R 3 independently represent a hydrogen atom, a halogen atom, a
  • R 4 , R 5 and R 6 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • a viscoelastic, solid textile treatment surfactant composition containing, based on its total weight
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • R, R 2 and R 3 independently represent a hydrogen atom, a halogen atom, a
  • R 4 , R 5 and R 6 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • 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 ⁇ 2 Hz and 10 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 (each at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz).
  • the viscoelastic, solid surfactant composition incorporates all the advantages of a liquid composition, provides an aesthetic product form with a good dissolution profile in the context of textile treatment with excellent performance profile on the substrate.
  • WO 2010/108002 discloses structured liquid surfactant compositions which contain not more than 1% by weight of a benzylidenalditol compound as a structuring agent. Viscoelastic, solid surfactant compositions containing benzylidenalditol compounds are not described therein.
  • the viscoelastic, solid surfactant composition of the present invention is storage and dimensionally stable.
  • the said viscoelastic, solid surfactant composition has 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.
  • Rotational rheometer for example TA-Instruments, type AR G2, Malvern "Kinexus”, performed using a cone-plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C.
  • 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 constant below a certain shear stress amplitude or deformation amplitude, above which 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. between 0.01 Hz and 10 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 a deformation amplitude of 0, 1% has proven to be 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. This definition applies inter alia to "organic bleach activators" as a chemical compound mutatis mutandis.
  • 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.
  • 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 come tissue or textiles (such as eg clothes) in question.
  • the portions according to the invention are preferably used to provide a surfactant-containing liquor in the course of mechanical cleaning processes, as are carried out, for example, by a washing machine for textiles.
  • At least one refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more In the context of components of the compositions described herein, this indication does not refer to the absolute amount
  • at least one inorganic base therefore means, for example, one or more different inorganic bases, ie 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.
  • compositions of the invention preferably have a flow limit.
  • the yield stress refers to the smallest stress (force per area) above which a plastic substance behaves rheologically like a liquid. It is given in Pascal (Pa).
  • the flow limit of the compositions was measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called
  • Shear stress in the course of 10 minutes with 10 points per shear stress decade from the smallest possible value (eg 2 mPa) to eg 10 Pa can be increased.
  • the time interval is chosen such that the measurement is carried out "quasi-statically", ie that the deformation of the sample can be brought into equilibrium for every given shear stress value.As a function of this shear stress, the equilibrium deformation ⁇ of the sample is measured plotted log plot against the shear stress If the investigated sample has a yield point, you can clearly see two areas in this plot differ. Below a certain shear stress, one finds a purely elastic one
  • the solid-form viscoelastic composition of the present invention preferably has a yield value in the range of 2.5 to 100 Pa, more preferably 3 to 80 Pa, as measured by rotational rheometer, 40 mm diameter cone-and-plate measuring system and 2 ° opening angle at a temperature of 20 ° C.
  • 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. unit used in water treatment for turbidity measurements, e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for cloudy surfactant compositions, while low values are determined for clear, transparent surfactant compositions.
  • 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 filled in a 10 ml measuring cuvette with cap 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. For this purpose, first a reference sample (water, demineralized) in a photometer (Fa. Specord S 600 from Analytikjena) with a transparent in the spectrum to be examined cuvette (layer thickness 10 mm) measured. Subsequently, the cuvette with a sample of the invention
  • the transparent surfactant composition of the present invention has a transmission (20 ° C) of more preferably at least 25%, more preferably at least 30%, more preferably at least 40%, especially at least 50%, most 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 surfactant composition according to the invention contains, based on the total weight thereof, a total amount of from 10 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 10 to 65% 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, more preferably 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% by weight , more preferably from 25 to 65% by weight, more preferably from 25 to 60% by weight, even more preferably from 30 to 70% by weight, more preferably from 30 to 65% by weight, more preferably from 30 to 60% by weight. % of at least one surfactant.
  • Surfactant compositions are also suitable for textile treatment, but especially for use in a washing machine for textile washing.
  • the surfactant composition contains at least one anionic surfactant and optionally additionally at least one nonionic surfactant.
  • a preferred viscoelastic, solid surfactant composition according to the invention is characterized in that it contains at least one anionic surfactant.
  • Surfactant compositions with anionic surfactant are suitable for the washing of textiles, more preferably for use in a washing machine for textile washing.
  • anionic surfactant when the surfactant composition according to the present invention contains anionic surfactant, it is again preferable that, based on the total weight of the composition, anionic surfactant is contained in a total amount of 5 to 70% by weight, more preferably 5 to 60% by weight, more preferably 10 to 70% by weight. %, in particular 10 to 60 wt .-%, particularly preferably from 10 to 40 wt .-%, more preferably from 25 to 40 wt .-%, is contained.
  • the anionic surfactant used may preferably be sulfonates and / or sulfates.
  • surfactants of the sulfonate type are preferably C9-i3-alkylbenzenesulfonates,
  • Olefin sulfonates i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • compositions according to the invention comprise as anionic surfactant at least one compound of the formula (T1)
  • 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 Ci2-Ci5-alkyl sulfates and Cw-cis-alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of the straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11- Alcohols with an average of 3.5 moles of 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.
  • the surfactant composition comprises a monoethanolamine-neutralized alkylbenzenesulfonic acid, especially C9-13-alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.
  • a preferred surfactant composition contains 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.
  • the surfactant composition contains at least one nonionic surfactant.
  • the at least one nonionic surfactant may be any known nonionic surfactant suitable for the purpose of this invention.
  • Surfactant compositions as nonionic surfactant at least one fatty alcohol alkoxylate having the following formula (T2), wherein R 'is a linear or branched Cs-ds-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.
  • R ' is a linear or branched, substituted or unsubstituted alkyl radical.
  • R ' is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular 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 formula (T2) is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index m of the formula (T2) is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • Surfactant composition may include mixtures of nonionic surfactants having different degrees of ethoxylation.
  • 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.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, Csn alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and Ci 2 -8-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. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants which have been obtained from C 6-2o -monohydroxyalkanols or C 6-2o-alkylphenols or C 16-2o-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 (Ci6-2o-alcohol), preferably a cis-alcohol and at least 12 moles, preferably at least 15 moles and in particular 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.
  • the surfactant composition of the present invention may contain, as a nonionic surfactant, amine oxide.
  • amine oxide in principle all amine oxides established for this purpose in the prior art are compounds which have the formula RR 2 R 3 NO, wherein each R, R 2 and R 3 independently of the others is an optionally substituted hydrocarbon chain having 1 to 30 carbon atoms , usable.
  • Particularly preferred amine oxides are those wherein R 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.
  • the degree of oligomerization x, the distribution of monoglycosides and 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.
  • particularly preferred viscoelastic, solid-form surfactant compositions contain, based in each case on the total weight, a total amount of
  • Very particular preferred viscoelastic, solid surfactant compositions according to the invention comprise, in addition to water and said benzylidene-alditol compound, at least one surfactant combination as described below for the compositions (A) to (D):
  • (A) viscoelastic, solid surfactant composition containing as surfactant in each case based on the total weight of the composition at least in each case a total amount of 10 to 60 wt .-% of at least one anionic surfactant, wherein at least one C9-i3-alkylbenzenesulfonate is contained as 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 From 10 to 60% by weight of at least one anionic surfactant, the anionic surfactant containing at least 5 to 60% by weight of at least one C9-i3-alkylbenzenesulfonate, 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 surfactant composition containing as surfactant in each case based on the total weight of the composition at least in each case a total amount of
  • 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 surfactant composition according to the invention contains, in addition to the anionic and nonionic surfactant, at least one polyalkoxylated polyamine.
  • 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 of 1: 0.5 to 1: 1, 5, in particular in the range of 1: 0.7 to 1: 1.
  • the ratio of primary to tertiary amino groups in the polyamine is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 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.
  • 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.
  • Particularly preferred are ethylene groups, 1, 2-propylene groups, 1, 3-propylene groups, and their
  • 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 must be alkoxy group-substituted.
  • 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 an O-C10, in particular C1-C3-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 the use of polyalkoxylated
  • 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 additionally contains at least one soil-release active ingredient.
  • Dirt-removing substances are often referred to as "soil-release” agents or because of their ability to render the treated surface, preferably textiles, dirt-repellent, "soil repellents". Because of their chemical similarity to polyester fibers particularly effective soil release agents, but can also show the desired effect in fabrics of other materials are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing polyesters 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 O- to C4-alkyl groups are end-capped.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of 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. From the European patent application EP 272 033 at least partially by Ci-4-alkyl or acyl radicals end phenomenonver claimed polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units are known. European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European
  • Patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C2-4-glycol units.
  • Surfactant composition at least one soil release-capable polyester, comprising the structural units E-1 to E-I l l or E-l 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 with a group -SO3M
  • M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or Tetraalkylammonium, where the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl or C 2 -C 10 -hydroxyalkyl radicals or any desired mixtures thereof,
  • R 1 , 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
  • 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 gmol, particularly preferably from 1,200 to 12,000 g / mol.
  • solid polyesters which have softening points above 40 ° C. are preferably used as part of the particle of the second type; 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 surfactant composition of the present invention may additionally contain at least one enzyme.
  • 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, ⁇ -glucosidase, carrageenase, Perhydrolase, oxidase, oxidoreductase and their mixtures.
  • 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 are available for use in washing or
  • Detergents improved variants available, 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
  • 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 name Duramyl® and Termamy Dultra, from Genencor under the name Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • B. amyloliquefaciens ⁇ -amylase is sold by Novozymes under the name BAN®, and variants derived from B. stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from Novozymes.
  • the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • fusion products of all the molecules mentioned can be used.
  • 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
  • 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.
  • 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.
  • Novozymes under the trade name Celluzyme® offered.
  • the products Endolase® and Carezyme®, which are also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft®, Renozyme® and Celluclean®. Continue to be used
  • 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. CBS 670.93 from the company Genencor under the trade name Puradax® is available.
  • Further commercial products of Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention.
  • Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
  • hemicellulases include, for example, mannanases, 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,
  • enzymes suitable for this purpose 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 weight percent 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 .-% in this portion.
  • builders In addition, builders, complexing agents, optical brighteners (preferably in portions for textile washing), pH adjusters, perfume, dye, can be used as additional ingredients.
  • Color transfer inhibitor (dye transfer inhibitor) or mixtures thereof in the
  • 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 viscoelastic, solid-form surfactant composition according to the invention in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight, 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-form composition according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • 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 preferably in a proportion of 0.3 to 10 wt .-%, in particular from 0.5 to 8 wt .-%, particularly from 0.7 to 6.0 wt .-%, particularly preferably 0.8 to 5 , 0 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 tenid compositions according to the invention preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.3 to 8% by weight, very particularly preferably from 0.5 to 4.0% by weight. %, in each case based on the total weight of the composition.
  • 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 particularly preferably from 1200 to 5000 g / mol, may again be preferred from this group.
  • the viscoelastic, festformigen surfactant compositions of the invention may as a builder also crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is 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 O: SiO 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 in dissolution and secondary wash properties.
  • 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 '.
  • 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.
  • PVP / PVI copolymer for example, from BASF under the name Sokalan® HP 56.
  • Another extremely preferred color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF are.
  • 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 having a mean diameter Xso, 3 (volume average) of 0.1 to 200 ⁇ , preferably from 1 to 100 ⁇ , more preferably from 5 to 80 ⁇ , more preferably from 10 to 50 ⁇ and in particular from 15 to 40 [im have.
  • 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 significant amounts of the at least one perfume in the capsule core, so that a very intense fragrance is provided when damaged or when the capsule is opened.
  • 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 by reacting 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 e.g. at least one
  • Suitable protective colloids are e.g. 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 group-containing water-soluble polymers containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, as well as polymers of N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids,
  • 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.
  • microcapsules Preference for use microcapsules have average diameter Xso, 3 in the range of 1 to 100 ⁇ , preferably from 5 to 95 ⁇ , in particular from 10 to 90 ⁇ , for example from 10 to 80 ⁇ .
  • 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 e.g. Bismuth oxychloride and perglaze pigments based on mica and 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
  • Pearlescent pigments in conjunction with metal oxides the mica, predominantly muscovite or phlogopite, coated with a metal oxide.
  • Suitable metal oxides are i.a. ⁇ 2, CteCb and Fe2Ü3.
  • interference pigments and color luster pigments are obtained as pearlescent pigments according to the invention.
  • 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 ⁇ , particularly preferably between 10.0 and 60.0 ⁇ .
  • speckles are to be understood as meaning macroparticles, in particular macrocapeins, 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.
  • the matrix formation takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is in the prior art as well as the
  • 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 viscoelastic, solid surfactant composition necessarily contains, based on the total amount of the composition, a total amount of more than 1% by weight of said benzylidene alditol. Due to the stereochemistry of the alditols it should be mentioned that
  • Both said Benzylidenalditole according to the invention in the L-configuration or in the D configuration or a mixture of both are suitable. Due to the natural availability, the benzylidenalditol compounds according to the invention are preferably used in the D configuration. It has been found to be preferred when the alditol skeleton of the in the
  • Benzylidenalditol compound according to formula (I) of D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol derives.
  • surfactant compositions which are characterized in that R, R 2 , R 3 , R 4 , R 5 and R 6 according to Benzylidenalditol compound of formula (I) independently of one another hydrogen, methyl, ethyl, chlorine, fluorine or Methoxy, preferably a hydrogen atom, mean.
  • n according to benzylidenalditol compound of the formula (I) is preferably 1.m according to the benzylidenalditol compound.
  • Formula (I) is preferably 1.
  • the surfactant composition according to the invention contains
  • Benzylidenalditol compound of the formula (I) at least one compound of the formula (1-1)
  • R 1 , R 3 , R 4 , R 5 and R 6 are as defined in claim 1. Most preferably, according to formula (1-1), R, R 2 , R 3 , R 4 , R 5 and R 6 are independently
  • Hydrogen atom methyl, ethyl, chlorine, fluorine or methoxy, preferably for a
  • the benzylidenalditol compound of formula (I) is selected from 1,3,3,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-O- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-chlorobenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof.
  • the benzylidenalditol compound of the formula (I) present in the viscoelastic, solid surfactant composition is preferably in a total amount of more than 1.5% by weight, in particular more than 2.0% by weight, based on the total weight of the composition. contain.
  • the benzylidenalditol compound of the formula (I) contained in the surfactant composition is in a total amount of more than 1.6% by weight or more than 1.7% by weight or more than 1 relative to the total weight of the composition , 8 wt .-%, or more than 1, 9 wt .-%, or more than 2.0 wt .-%, or more than 2.1 wt.%, Or more than 2.2 wt .-%, or more than 2.3 wt%, or more than 2.4 wt%, or more than 2.5 wt%.
  • the benzylidenalditol compound of the formula (1-1) contained in the viscoelastic, solid surfactant composition is preferably in a total amount of more than 1.3% by weight, more preferably more than 1.5% by weight, based on the total weight of the composition. more preferably more than 2.0% by weight.
  • the benzylidene-alditol compound of the formula (1-1) contained in the Tendis composition is in a total amount of more than 1.65% by weight or more than 1.7% by weight or more, based on the total weight of the composition as 1, 8 wt .-%, or more than 1, 9 wt .-%, or more than 2.0 wt .-%, or more than 2.1 wt.%, or more than 2.2 wt. %, or more than 2.3 wt .-%, or more than 2.4 wt .-%, or more than 2.5 wt .-%, included.
  • the benzylidenealditol compound of the formula (I) contained in the surfactant composition is preferably in a total amount of at most 15% by weight based on the total weight of the composition. , in particular of at most 10 wt .-%, use.
  • the benzylidene-alditol compound of the formula (1-1) contained in the surfactant composition is preferably in a total amount of at most 15% by weight, especially at most 10% by weight, based on the total weight of the composition. -%, use.
  • 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 between 0 and 70 wt .-%, in particular between 0 and 60 wt .-%, more preferably between 0 to 40 wt .-%, particularly preferred between 0 to 25 wt .-% is included.
  • the proportion of water in the surfactant composition is most preferably 20% by weight or less, again more preferably 15% by weight or less, still more preferably 12% by weight or less, especially between 20 and 4% by weight.
  • the data in% by weight relate to the
  • 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
  • organic solvent in a total amount of 5 to 40 wt .-%, in particular from 10 to 35 wt .-%, is included.
  • 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 consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 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.
  • 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, ichangine, 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, ichangine, 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
  • the viscoelastic, solid surfactant composition can be prepared by first comprising a liquid composition containing, based on the total weight thereof
  • the heated liquid composition in a mold preferably in a cavity of a mold and given in said form below the sol-gel transition temperature to form a viscoelastic, solid shaped body is cooled.
  • 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.
  • 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 contain at least two different viscoelastic, solid surfactant compositions of the first subject of the invention to form at least two phases, preferably at least two differently colored phases.
  • a trough molding as a first phase can be prepared, in the trough of which a second viscoelastic, solid surfactant composition of the first subject of the invention is introduced as a second phase.
  • the molded body of different, viscoelastic, solid compositions are formed, which are 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 Muldenformkorpers this embodiment preferably have an average thickness of at most 5 mm, in particular of at most 2 mm, more preferably of at most 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).
  • powdered solid In order to prevent sticking together of individual moldings which are located together in one packaging, it may be preferable to remove the moldings with a powdered solid.
  • 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 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
  • viscoelastic, solid surfactant composition of the first subject of the invention having a weight of from 1 to 80 g, especially from 1 to 70 g, more preferably from 1 to 50 g preferably from 1 to 30 g, in particular 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.
  • 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 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 .-%, in particular from 15 to 70 wt .-%, is contained, and
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • R, R 2 and R 3 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • R 4 , R 5 and R 6 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • (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
  • surfactant (I) 10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant, preferably at least one C9-i 3-alkylbenzenesulfonate is contained, and
  • 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
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • the shaped body is preferably coated with water-soluble material. Such 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 wall delimited by walls (eg by a film), which can also exist without the material to be dispensed (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, if at 20 ° C 0.1 g of the material with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm, beaker 1000mL low form the company. Schott, Mainz) within Dissolve 600 seconds in 800 mL of water so that no single solid particles of the material are visible to the naked eye.
  • 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 ⁇ ) are determined 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.
  • 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
  • the water-soluble material may additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, Polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.
  • 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 mixtures thereof, with itaconic acid being preferred.
  • 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 for the provision of the Pouch walls has a preferred thickness in a range of 65 to 180 ⁇ , in particular from 70 to 150 ⁇ , more preferably 75 to 120 ⁇ on.
  • water-soluble material of the coating of the shaped body of the portion or the walls of the pouch of the portion is preferably incorporated to increase the product safety a bittering agent.
  • 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 surfactant composition containing based on the
  • n 0 or 1, preferably 1,
  • n 0 or 1, preferably 1,
  • R, R 2 and R 3 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • R 4 , R 5 and R 6 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a
  • 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 ⁇ 2 Hz and 10 Hz is at least two times 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,
  • Olefinsulfonaten Ci2-is-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof, is included.
  • Composition according to point 1 to 4 characterized in that as surfactant at least one compound of formula (T1) is contained,
  • 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 + ).
  • composition according to one of the items 1 to 6, characterized in that it contains as surfactant at least one nonionic surfactant of the formula (T2) in the
  • R 2 is a linear or branched Cs-Os-alkyl radical, an aryl radical or alkylaryl radical, XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO)
  • EO ethylene oxide
  • PO propylene oxide
  • n stands for integers from 1 to 50.
  • composition according to one of the items 1 to 9 characterized in that R, R 2 , R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.
  • R, R 2 , R 3 , R 4 , R 5 and R 6 are as defined in item 1.
  • Composition according to one of the items 1 to 12 characterized in that the Benzylidenalditol compound of formula (I) in a total amount of more than 1, 5 wt .-%, in particular more than 2.0 wt .-%, is included , Composition according to one of the items 1 to 13, characterized in that water in a total amount between 0 and 45 wt .-%, in particular between 0 and 25 wt .-%, is included.
  • 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 15 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.
  • 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 it has a yield point in the range of 2.5 to 100 Pa, more preferably 3 to 80 Pa, measured with a rotary rheometer, a cone-plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C.
  • Composition according to one of the preceding points characterized in that the composition is transparent.
  • Molded body is cooled.
  • Denatonium benzoate 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001
  • Perfume dye, protease, 1, 7 1, 7 1, 5 2.6 1, 0 2.6 amylase, lipase, cellulase, (without (without
  • optical brightener dye optical brightener dye
  • Liquid detergent of Table 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.
  • the molded articles prepared in this way each had a storage modulus of the order of 10 6 Pa, which was at least ten times larger than the loss modulus.
  • Shaped body F2 was transparent with a transmission of 61.3%.

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

Abstract

L'invention concerne une composition tensioactive viscoélastique, solide pour le traitement des textiles, contenant, par rapport à son poids total, (i) une quantité totale de 10 à 70 % en poids d'au moins un tensioactif et(ii) une quantité totale supérieure à 1 % en poids d'au moins un composé du benzylidène-alditol de formule (I) dans laquelle *- représente une simple liaison covalente entre un atome d'oxygène de la structure de base alditol et le radical prévu, n représente 0 ou 1, de préférence 1, m représente 0 ou 1, de préférence 1, R1, R2 et R3 représentent, indépendamment les uns des autres, un atome d'hydrogène, un atome d'halogène, un groupe C1-C4-alkyle, un groupe cyano, un groupe nitro, un groupe amino, un groupe carboxyle, un groupe hydroxy, un groupe -C(=O)-NH-NH2, un groupe -NH-C(=O)-(C2-C4-alkyle), un groupe C1-C4-alcoxy, un groupe C1-C4-alcoxy-C2-C4-alkyle, deux des radicaux forment, ensemble avec le reste de la molécule, un cycle de 5 ou 6 chaînons, R4, R5 et R6 représentent, indépendamment les uns des autres, un atome d'hydrogène, un atome d'halogène, un groupe C1-C4-alkyle, un groupe cyano, un groupe nitro, un groupe amino, un groupe carboxyle, un groupe hydroxy, un groupe -C(=O)-NH-NH2, un groupe -NH-C(=O)-(C2-C4-alkyle), un groupe C1-C4-alcoxy, un groupe C1-C4-alcoxy-C2-C4-alkyle, deux des radicaux forment, ensemble avec le reste de la molécule, un cycle de 5 ou 6 chaînons et (iii) de l'eau. La composition représente une forme bien soluble, esthétiquement attrayante et stable au stockage d'une composition solide pour la préparation de bains tensioactifs.
EP18732005.6A 2017-06-16 2018-06-12 Composition tensioactive viscoélastique, solide, présentant une teneur élevée en tensioactif Pending EP3638756A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102017210141.5A DE102017210141A1 (de) 2017-06-16 2017-06-16 Portion zur Bereitstellung tensidhaltiger Flotten
DE102017210143.1A DE102017210143A1 (de) 2017-06-16 2017-06-16 Viskoelastische, festförmige Tensidzusammensetzung
DE102017223456.3A DE102017223456A1 (de) 2017-12-20 2017-12-20 Viskoelastische, festförmige Tensidzusammensetzung mit hohem Tensidgehalt
PCT/EP2018/065466 WO2018229036A1 (fr) 2017-06-16 2018-06-12 Composition tensioactive viscoélastique, solide, présentant une teneur élevée en tensioactif

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EP3638756A1 true EP3638756A1 (fr) 2020-04-22

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EP (1) EP3638756A1 (fr)
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WO (1) WO2018229036A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018217340A1 (de) * 2018-10-10 2020-04-16 Henkel Ag & Co. Kgaa Gelförmige Formkörper zur Beduftung von Textilien im Waschprozess
DE102022203708A1 (de) * 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit

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DE102017210143A1 (de) * 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Viskoelastische, festförmige Tensidzusammensetzung
WO2018229037A1 (fr) * 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Composition tensioactive solide, viscoélastique présentant une teneur élevée en tensioactif

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US11261407B2 (en) 2022-03-01
KR102510191B1 (ko) 2023-03-15
US20200115657A1 (en) 2020-04-16
KR20200019704A (ko) 2020-02-24
WO2018229036A1 (fr) 2018-12-20

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