DE102008052678A1 - New nanoparticle comprising a core from an inorganic material, a silane group containing intermediate layer and a polyoxyalkylene monoamine comprising external layer, useful for the reduction of resoilability on textile or hard surfaces - Google Patents

Abstract

Nanoparticle comprising a core from an inorganic material, at least a silane group containing intermediate layer and at least a polyoxyalkylene monoamine comprising external layer, is new. Independent claims are included for: (1) a textile or surfaces treating agent comprising at least a surfactant and the nanoparticle; (2) an adhesive agent, sealant or coating agent comprising at least a hardenable resin component and the nanoparticle; (3) an article comprising at least a component, which is adhered, sealed or coated with the adhesive agent, sealant or coating agent; (4) the preparation of the nanoparticle; and (5) impact modification and/or improvement of the tensile shearing strength of the adhesive comprising adding adhesive, before hardening with the nanoparticle.

Description

The The present invention relates to multilayer nanoparticles which Cores of an inorganic material, at least one silane group comprehensive interlayer and at least one polyoxyalkylene monoamines have comprehensive outer layer. Other items of the present invention are textile or surface treatment agents and adhesives, sealants or coating compositions containing the invention Nanoparticles include, as well as a method for producing the inventive Nanoparticles.

nanoparticles are now used in many areas of technology, to give materials special properties. That's it important that the particular nanoparticles used targeted to the particular Requirements of the respective purpose of use and the respective Application environment can be customized. A possibility in the Prior art, a targeted adaptation of the nanoparticles to the respective Application purpose and the respective application environment is the surface of the nanoparticles with organic To modify molecules.

That's how it describes WO 2006/01680 A1 Coating compositions containing particles modified with reactive groups and polymer chains, wherein the polymer chains in particular ethylene oxide, (meth) acrylic acid, (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, phosphorylcholine, glycidyl contain (meth) acrylate or saccharide monomer units.

The WO 2003/047753 A1 relates to a microparticulate material comprising nanoparticulate cores of an inorganic material having on its surface oligomeric or polymeric structures containing non-acidic, nucleophilic groups, the cores having an interaction of the non-acidic, nucleophilic groups with at least one other Component containing electrophilic groups are agglomerated.

N. Joubert, C. Delaite, E. Bourgeat-Lami and P. Dumas (Macromol Rapid Commun. 2005, 602-607) describe the modification of silica nanoparticles by reaction with prehydrolyzed 3-glycidoxypropyltrimethoxysilane oxide and subsequent ring-opening polymerization of oxirane monomers at the particle surface.

Fujiki et al. (Journal of Macromolecular Science Part A, 2000, 34 (4) 357-377) describe the modification of silica nanoparticles with dendrimeric structures, wherein the dendrimeric structures are obtained by sequential reaction of acrylic acid esters with diamines on the particle surface.

The US 2007/0275042 A1 discloses curable compositions containing from 1 to 20 percent by weight of surface-modified nanoparticles, which comprise ethylenically unsaturated groups and have an average particle diameter of less than 20 nm.

The US 2008/0021147 A1 describes a method for producing a dispersion of silica nanoparticles in which the silica nanoparticles having a particle size of 1 to 500 nm are reacted either with a specific amount of a branched or hyperbranched oligomer, which has at least two groups reactive with the nanoparticles, or reacting the silica nanoparticles with a predetermined amount of a mixture of said branched or hyperbranched oligomer with a film forming polymer and a low molecular weight coupling reagent or a mixture of a film forming polymer with a low molecular weight coupling reagent.

regardless The prior art still has a need for new and beneficial inorganic nanoparticles, the materials can give special properties and in particular due to their easy dispersibility and good processability in Solvents or other carrier media and have low sedimentation and / or crosslinking tendencies.

Surprisingly has now been found that by certain surface modifications of inorganic nanoparticles whose sedimentation and / or crosslinking tendencies can be reduced and stable dispersion of nanoparticles achieved in solvents or other carrier media become. The surface modification of the inorganic nanoparticles is thereby realized by a method that is easier Perform way and can be varied widely so as to allow new surface-modified nanoparticles tailor-made for different applications to provide.

object The present invention therefore includes nanoparticles containing cores of an inorganic material comprising at least one silane group Intermediate layer and at least one polyoxyalkylene monoamines comprising outer Layer, and a method for producing the inventive Nanoparticles.

The Nanoparticles of the invention are in particular Way to suitable as a component of textile or surface treatment agents the removal of dirt from textile or hard surfaces to improve and / or reduce their Wiederzusmutzbarkeit.

object Therefore, the present invention also includes textile or surface treatment agents comprising at least one surfactant and the invention Nanoparticles and the use of the invention Nanoparticles for improving soil release from and / or Reduction of re-fouling on textile or hard Surfaces.

The nanoparticles of the invention are still suitable as a component of adhesives, sealants or Coating compositions whose mechanical properties, such as their tensile shear strength and / or their impact resistance, to improve.

One Another object of the present invention is therefore an adhesive, Sealant or coating agent comprising at least one curable Resin component and nanoparticles of the invention, and an article containing at least one component, with the mentioned adhesive, sealant or coating agent glued, sealed, or coated.

Also The present invention is a process for impact modification and / or for improving the tensile shear strength of an adhesive, wherein the adhesive before curing with the invention Nanoparticles is added.

As already described above contain the inventive Nanoparticles Cores made of an inorganic material, at least a silane-containing intermediate layer and at least one Polyoxyalkylene monoamines comprising outer layer.

Under The term "nanoparticles" are within the meaning of the present Invention Particles having an average particle diameter of 1 to 500 nm, the particles being separated in the form Particles or as an agglomerate of several particles may be present.

Under the term "mean particle diameter" in the context of the present invention preferably the volume average D50 particle diameter to understand the usual Method can be determined, for example by light scattering. The volume average D 50 particle diameter is that point in the particle size distribution at which 50% by volume the particles have a smaller and 50% by volume of the particles a larger one Have diameter.

In a preferred embodiment of the invention the nanoparticles according to the invention have a middle Particle diameter of 15 nm to 250 nm. In particular it is preferred that the lower limit of the average particle diameter the nanoparticles according to the invention at 20 nm, preferably at 25 nm and in particular at 30 nm. The upper limit the average particle diameter of the invention Nanoparticles are preferably at 200 nm, preferably at 150 nm and in particular at 100 nm.

The nanoparticles of the invention have a multilayer Structure on and contain a core of an inorganic material.

Generally For example, the inorganic material of the cores may be selected be made of metals, oxides, hydroxides, carbonates, sulfates and Phosphates. It can also be mixed forms of oxides, hydroxides and carbonates, such as basic carbonates or basic Oxides are present.

In In a preferred embodiment, the inorganic Material of the cores of the nanoparticles according to the invention selected from oxides or hydroxides of silicon, cerium, Cobalt, chromium, nickel, zinc, titanium, iron, yttrium, zirconium and / or Aluminum.

Particular preference is given to zinc oxide, aluminum oxides or hydroxides and also SiO ₂ or the oxide forms of silicon referred to as "silicic acid" or Anglo-Saxon as "silica".

invention Nanoparticles that have a core of silica are in the sense of the present invention particularly preferred.

The Cores of the nanoparticles of the invention from a inorganic material, hereinafter referred to as inorganic cores, have an average particle size, which is compatible with the intended use. The lower limit the size of the inorganic nuclei is on the one hand by their manufacturability and on the other hand by their influence on the material properties of the nanoparticles according to the invention given.

A technically appropriate lower limit of the average Particle size of the inorganic nuclei is included 5 nm, preferably at 10 nm and especially at 15 nm. The upper limit the inorganic nuclei is determined by the mean particle size limited nanoparticles of the invention, which is why the upper limit of the mean particle size of the inorganic nuclei is chosen so that the maximum Expansion of the inorganic nuclei in each spatial direction smaller is as the average particle diameter of the invention Nanoparticles.

Especially Depending on the size of the core, inorganic cores are preferred. whose average particle diameter is between 5 and 100 nm, preferably between 10 and 80 nm and in particular between 20 and 60 nm.

The maximum expansion of the inorganic nuclei in each spatial direction can, for example, by statistical evaluation (electron) microscopic Recordings are received.

The inorganic cores are particularly preferably monodisperse cores of spherical shape. The production of such cores is known to the person skilled in the art and can be carried out in particular with inorganic cores of silica via sol-gel processes. A suitable sol-gel process in this context is, for example, the Stöber process [cf. W. Stöber et al. in J. Colloid and Interface Science 26, 62 (1968) and 30, 568 (1969) ]. A general overview of sol-gel processes for the production of inorganic nanostructures can H. Schmidt, Chemistry in Our Time, 35 (3) 176-184 (2001) be removed.

Most preferably, the preparation of the inorganic cores is carried out by reacting one or more alkali metal silicates, such as sodium silicate, in the presence of an acidic cation exchanger, whereby colloidal dispersions of silica particles can be obtained as a rule. Such a process is for example in U.S. Patent 2,631,134 described. Colloidal dispersions of silica particles are commercially available for example under the trade name Levasil ^® (Bayer AG), Klebosol ^™ (Clariant) and Ludox ^® (DuPont) sold by the companies mentioned.

As already described above contain the inventive Nanoparticles a silane-containing intermediate layer. These Interlayer joins the outer polyoxyalkylene monoamines Layer with the inorganic cores. Preferably, the linkage takes place the inorganic cores with the silane groups comprising intermediate layer and the linkage of the silane-containing intermediate layer with the polyoxyalkylene monoamines comprising outer Layer by at least one covalent bond.

Also may be the linkage of the silane-containing interlayer with the inorganic nuclei by non-covalent interactions, such as electrostatic interaction or by complex formation caused interactions occur.

Under a "silane group" is within the meaning of the present Invention preferably a divalent group to understand the at least a silicon atom covalently bonded to at least one oxygen atom and is connected to at least one carbon atom.

Especially preferred is a "silane group" in the sense of the present invention to understand a divalent group, the at least one silicon atom which exclusively with one or more carbon atoms and one or more Oxygen atoms are covalently bound, with the proviso that the at least one silicon atom having at least one oxygen atom and covalently linked to at least one carbon atom.

For the purposes of the present invention, a "silane group" is to be understood as meaning a divalent group which comprises only one silicon atom, which excludes only one silicon atom covalently bonded to one or more carbon atoms and one or more oxygen atoms, with the proviso that only one silicon atom is covalently bonded to at least one oxygen atom and to at least one carbon atom.

In a preferred embodiment of the invention are the Polyoxyalkylene monoamines of the outer layer over their amino groups to the silane groups of the intermediate layer covalently bonded, wherein each silane group at least one hydroxyl group having covalently linked to a carbon atom of the silane group is.

The Silane group of the present invention may be linear or branched and preferably 2 to 100 carbon atoms, more preferably 4 to 50 carbon atoms and most preferably 6 to 20 Include carbon atoms. By the number of carbon atoms and the type and number of functional groups in the silane group can their properties and thus the properties the intermediate layer can be varied. That's the way it is for example possible the polarity and thickness of the intermediate layer to change specifically.

der Formel (Ib),

und/oder der Formel (Ic),

wobei
R¹ und R² unabhängig voneinander für eine lineare oder verzweigte gegebenenfalls substituierte C1-12 Alkylgruppe, eine lineare oder verzweigte gegebenenfalls substituierte C1-12 Alkoxygruppe, eine gegebenenfalls substituierte C6-12 Arylgruppe, eine gegebenenfalls substituierte C6-12 Cycloalkylgruppe oder für eine gegebenenfalls substituierte C8-12 Aralkylgruppe stehen,
R³, R⁴ und R⁵ unabhängig voneinander für Wasserstoff oder für eine gegebenenfalls substituierte C1-12 Alkyl-, C3-8 Cycloalkyl-, C2-5 Alkenyl-, C2-6 Alkinyl- C1-12 Heteroalkyl-, C2-8 Heterocycloalkyl- oder C2-12 Alkoxyalkylgruppe stehen,
R^3' für Wasserstoff, Halogen oder für eine gegebenenfalls substituierte C1-12 Alkyl- oder C1-12 Alkoxygruppe steht und
Y eine gegebenenfalls substituierte C6-12 Arylengruppe, eine gegebenenfalls substituierte C8-12 Aralkylengruppe, eine C5-12 gegebenenfalls substituierte Cycloalkylengruppe oder eine lineare oder verzweigte gegebenenfalls substituierte C1-18 Alkylengruppe ist, wobei die Kohlenstoffkette der Alkylengruppe durch nicht benachbarte Sauerstoff- oder Schwefelgruppen unterbrochen sein kann.In a further embodiment of the invention, the intermediate layer comprising at least one silane group comprises at least one structural unit selected from structural units of the formula (Ia),

of the formula (Ib),

and / or the formula (Ic),

in which
R ¹ and R ² independently represent a linear or branched optionally substituted C 1-12 alkyl group, a linear or branched optionally substituted C 1-12 alkoxy group, an optionally substituted C 6-12 aryl group, an optionally substituted C 6-12 cycloalkyl group, or an optionally substituted one C8-12 aralkyl group,
R ³ , R ⁴ and R ^{5 are} independently hydrogen or an optionally substituted C 1-12 alkyl, C 3-8 cycloalkyl, C 2-5 alkenyl, C 2-6 alkynyl, C 1-12 heteroalkyl, C 2-8 heterocycloalkyl or C2-12 alkoxyalkyl group,
R ^{3 'is} hydrogen, halogen or an optionally substituted C 1-12 alkyl or C 1-12 alkoxy group and
Y is an optionally substituted C6-12 arylene group, an optionally substituted C8-12 aralkylene group, a C5-12 optionally substituted cycloalkylene group or a linear or branched optionally substituted C1-18 alkylene group, wherein the carbon chain of the alkylene group is interrupted by nonadjacent oxygen or sulfur groups can be.

In a further preferred embodiment, R ¹ and R ² independently of one another are a li -linear C1-4 alkyl group, a C1-C4 alkoxy group or an optionally substituted C6-12 cycloalkyl group and / or R ^3, R ⁴ and R ⁵ independently represent hydrogen and / or Y is a linear C2-10 alkyl group, the carbon chain of the alkyl group may be interrupted by non-adjacent oxygen or sulfur groups.

R ^{3 '} in a particularly preferred embodiment of the invention is hydrogen.

Especially preferred is at the non-oxygen-terminated end of the structural unit of the formula (Ia), the formula (Ib) and / or the formula (Ic), respectively covalently bound the polyoxyalkylene monoamine via its amino groups, while at the oxygen-terminated end of the structural unit of the formula (Ia), the formula (Ib) and / or the formula (Ic), respectively the core bonded from an inorganic material, in particular covalently bound.

As already described above contain the inventive Nanoparticles an outer layer, the polyoxyalkylene monoamines wherein the amino group of the polyoxyalkylene monoamines is especially preferably a primary amino group.

The outer one Layer of nanoparticles according to the invention can thereby also include mixtures of different polyoxyalkylene monoamines.

The polyoxyalkylene monoamines mentioned particularly preferably comprise ethylene oxide and / or propylene oxide units.

In the context of the present invention, an ethylene oxide unit (EO) is a unit of the general formula (II) * -CH ₂ -CH ₂ -O- * Formula (II) and for the purposes of the present invention, a unit of the general formula (III) is understood to mean a propylene oxide unit (PO). * -CH ₂ -CH (CH ₃ ) -O- * Formula (III) to understand.

It It is known that the hydrophilicity or hydrophobicity of polyoxyalkylene monoamines for example, about the ratio of ethylene oxide units (EO) can be controlled to propylene oxide units (PO)

In a particularly preferred embodiment of the invention is the ratio of ethylene oxide units (EO) too Propylene oxide units (PO) in the polyoxyalkylene monoamine between 30: 1 and 1:30, preferably between 10: 1 and 1:10, and most preferably between 6: 1 and 1: 6. In the areas mentioned, the Hydrophilicity or hydrophobicity of the invention Polyoxyalkylenmonoamins and thus the outer Layer of nanoparticles according to the invention effectively to be changed.

wobei R⁶ für eine lineare oder verzweigte, gegebenenfalls substituierte C1-10 Alkylgruppe steht, R⁷ für Wasserstoff oder eine Methylgruppe steht und m und n jeweils unabhängig voneinander für eine ganze Zahl von 0 bis 50 stehen, mit der Maßgabe das n + m ≥ 1 ist.Particularly preferred polyoxyalkylene monoamines in the context of the present invention are polyoxyalkylene monoamines of the general formula (IV)

wherein R ^{6 is} a linear or branched, optionally substituted C 1-10 alkyl group, R ^{7 is} hydrogen or a methyl group, and m and n are each independently an integer from 0 to 50, with the proviso that n + m ≥ 1 is.

In a preferred embodiment of the invention, the weight average molecular weight "M _w " of the polyoxyalkylene monoamines of the present invention is in the range of 500 to 10,000 g / mol, preferably in the range of 550 to 5000 g / mol and most preferably in the range of 600 to 2200 g / mol. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as standard.

Particularly preferred polyoxyalkylene monoamines according to the invention are available from Huntsman Corp. Texas sold under the trade name Jeffamine ^® M-600, Jeffamine ^® M-1000, Jeffamine ^® M-2005 and Jeffamine ^® M-2070th

• a) Bereitstellung nanopartikulärer Kerne aus einem anorganischem Material,
• b) Oberflächenfunktionalisierung der nanopartikulären Kerne mit Epoxygruppen durch Umsetzung der genannten Kerne mit mindestens einem Epoxysilan und
• c) Umsetzung der in Schritt b) erhaltenen Epoxy-funktionalisierten Kerne mit mindestens einem Polyoxyalkylenmonoamin, welches nur eine zu den Epoxygruppen der Epoxy-funktionalisierten Kerne reaktive funktionelle Gruppe aufweist.

A further subject of the present invention is a process for the preparation of the nanoparticles according to the invention, comprising the steps:

• a) providing nanoparticulate cores of an inorganic material,
• b) surface functionalization of the nanoparticulate cores with epoxy groups by reacting said cores with at least one epoxy silane and
• c) reacting the epoxy-functionalized cores obtained in step b) with at least one polyoxyalkylene monoamine which has only one functional group reactive with the epoxy groups of the epoxy-functionalized cores.

Under the term "nanoparticulate nuclei" in the context of the present invention, the "inorganic Cores "to understand.

Under The term "epoxysilane" is used in the context of the present invention Invention to understand a compound containing at least one silane group and at least one epoxy group, the term "silane group" being like is defined above.

wobei R⁸ für eine lineare oder verzweigte gegebenenfalls substituierte C1-4 Alkylgruppe oder eine gegebenenfalls substituierte C6-12 Arylgruppe steht,
R⁹ eine lineare oder verzweigte gegebenenfalls substituierte C1-6 Alkylgruppe ist, u gleich 0, 1 oder 2 ist und k für eine ganze Zahl von 1 bis 5 steht.Preferred epoxysilanes are selected from epoxysilanes of the general formula E- (I),

wherein R ^{8 is} a linear or branched optionally substituted C 1-4 alkyl group or an optionally substituted C 6-12 aryl group,
R ^{9 is} a linear or branched optionally substituted C 1-6 alkyl group, u is 0, 1 or 2 and k is an integer from 1 to 5.

Especially are 3-glycidyloxypropyltrimethoxysilane (GLYMO), 3-glycidyloxypropyltriethoxysilane (GLYEO), 3-glycidyloxypropyltri-n-propoxysilane, 3-glycidyloxypropyltri-isopropoxysilane, 3-glycidyloxypropyltri-n-butoxysilane and 3-glycidyloxypropyltri-iso-butoxysilane or mixtures thereof as epoxysilane in the context of the present invention prefers. A most preferred epoxysilane is 3-glycidyloxypropyltrimethoxysilane (GLYMO).

wobei R⁸, R⁹, k und u wie oben definiert sind.Furthermore, preferred epoxysilanes are also selected from epoxysilanes of the general formula E- (II),

wherein R ⁸ , R ⁹ , k and u are as defined above.

In particular, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred, which is sold commercially under the trade name Silquest ^® A-187 ^™ from Momentive Performance Materials.

to Surface functionalization of the nanoparticulate Cores with epoxy groups can in the sense of the invention Method mixtures of different epoxy silanes are used.

The epoxy silanes of the present invention react at least in part with the functional groups on the surface of the nanoparticulate cores, such as hydroxyl groups, to form a covalent bond between the at least one silicon atom of the respective epoxysilane and the functional groups located on the surface of the nanoparticulate cores. The reaction described usually leads to the release of water and / or a low molecular weight alcohol, which is why it is advantageous The reaction is to be carried out in such a way that water and / or the low molecular weight alcohol is removed from the reaction equilibrium. This can be done for example by the use of a water separator or an ion exchanger.

The in step b) of the method according to the invention performed epoxy functionalization of the nanoparticulate Cores takes place depending on the epoxysilane used preferably at temperatures of 20 to 120 ° C, at about 40 ° C to 80 ° C. The reaction time is also depending on the epoxysilane used preferably 10 minutes to 12 hours, especially 1 hour to 4 hours, with water and / or low molecular weight alcohols, such as isopropanol and / or methoxypropanol can be used as solvent can.

at in step c) of the method according to the invention carried out implementation of the epoxy-functionalized obtained in step b) Cores with at least one polyoxyalkylenemonoamine, which only one to reactive functional groups of the epoxy groups of the epoxy-functionalized cores Group, the reaction conditions, such as the pH or the reaction temperature, advantageously chosen so that at least 10%, preferably at least 40%, and most preferably at least 60% of all epoxy groups of the epoxy-functionalized cores with the polyoxyalkylene monoamine or the mixture of various polyoxyalkylene monoamines react to form a hydroxyl group.

Preferably it is the said reactive functional group the polyoxyalkylene monoamines to a primary amino group.

The obtained by the process according to the invention Nanoparticles can be isolated without solvent, without that thereby an irreversible networking and / or agglomeration the single nanoparticle occurs. By the solvent-free Isolation of the nanoparticles of the invention These can be easily stored and inexpensively be transported. Subsequently, the mentioned nanoparticles, for example in water and / or low molecular weight Alcohols such as isopropanol are easily redispersed, the redispersed nanoparticles have very little or no sedimentation tendencies exhibit.

By the choice of the respective epoxy silanes and polyoxyalkylene monoamines the process of the invention can be widely varied , resulting in new surface-modified nanoparticles for different purposes, characterized by a good processability in solvents or other carrier media.

Further Objects of the present invention is a textile or surface treatment agents comprising at least a surfactant and the nanoparticles of the invention, as well as the use of the nanoparticles according to the invention to improve soil release from and / or reduction resusability on textile or hard surfaces.

Under textile surfaces are within the scope of the present invention Surfaces of textile fabrics of wool, Silk, jute, hemp, cotton, linen, sisal, ramie; Rayon, cellulose ester, Polyvinyl derivatives, polyolefins, polyamides, viscose or polyester or mixtures thereof are particularly preferred. Very particularly preferred are textile surfaces in the context of the present invention made of cotton or cotton blend fabrics.

Under hard surfaces are within the scope of the present invention particularly preferred surfaces of porcelain, glass, ceramics, Plastic and / or metal to understand.

Of the Content of the nanoparticles according to the invention in The textile or surface treatment agent should be so be sized so that the surface treated with said agent is sufficiently covered. Preferably, the agent contains 0.01 to 20 wt .-%, particularly preferably 0.1 to 10 wt .-% and in particular From 0.5 to 5% by weight of the nanoparticles according to the invention, based on the total amount of the finished agent.

at the textile or surface treatment agent of the present invention Invention is in particular liquid or gel-like means.

The Textile or surface treatment agents of the present Invention includes in addition to the invention Nanoparticles also surfactants, these being preferably selected are made of anionic, cationic, ampholytic and nonionic Surfactants and any mixtures thereof.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R¹³-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R¹³ eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R¹⁴-O(CH₂-CH₂O)_x-OSO₃H, in der R¹⁴ eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether,
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel (E1-I),
  
  in der R¹⁴ bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R¹⁵ für Wasserstoff, einen Rest (CH₂CH₂O)_nR¹⁶ oder X, h für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR¹⁷R¹⁸R¹⁹R²⁰, mit R¹⁷ bis R¹⁹ unabhängig voneinander stehend für Wasserstoff oder einen C1 bis C4-Kohlenwasserstoffrest, steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel (El-II) R²⁰CO(AlkO)_hSO₃M (E1-II)in der R²⁰CO- für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, h für Zahlen von 0,5 bis 5 und M für ein Kation steht,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (E1-III)
  
  in der R²¹CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und i in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Olsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (E1-III) eingesetzt, in der R²¹CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht,
• – Amidethercarbonsäuren,
• – Kondensationsprodukte aus C₈-C₃₀-Fettalkoholen mit Proteinhydrolysaten und/oder Aminosäuren und deren Derivaten, welche dem Fachmann als Eiweissfettsäurekondensate bekannt sind, wie beispielsweise die Lamepon^®-Typen, Gluadin^®-Typen, Hostapon^® KCG oder die Amisoft^®-Typen.

Anionic surfactants usually comprise a water-solubilizing, anionic group such. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula R ¹³ -O- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R ^{13 is} a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• - linear alpha-olefin sulfonates having 8 to 24 carbon atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R ¹⁴ -O (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R ^{14 is} a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,
• Mixtures of hydroxysulfonates,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers,
• Sulfonates of unsaturated fatty acids having 8 to 24 C atoms and 1 to 6 double bonds,
• Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
• Alkyl and / or alkenyl ether phosphates of the formula (E1-I),
  
  in the R ^{14 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{15 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹⁶ or X, h is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ¹⁷ R ¹⁸ R ¹⁹ R ²⁰ , where R ¹⁷ to R ¹⁹ independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical,
• Sulfated fatty acid alkylene glycol esters of the formula (II-II) R ²⁰ CO (AlkO) _h SO ₃ M (E1-II) in the R ²⁰ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , h for numbers from 0.5 to 5 and M is a cation,
• Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)
  
  in which R ²¹ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and i in total 0 or numbers from 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (E1-III) are used in which R ²¹ CO is a linear acyl radical having 8 to 18 carbon atoms,
• - amide ether carboxylic acids,
• - Condensation products of C ₈ -C ₃₀ fatty alcohols with protein hydrolysates and / or amino acids and de ren derivatives, which are known in the art as Eiweissfettsäurekondensate, such as the Lamepon ^® types, Gluadin ^® types, Hostapon ^® KCG or the Amisoft ^® types.

preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and -dialkylester having 8 to 18 C-atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerisulfates, alkyl and Alkenyletherphosphate and protein fatty acid condensates.

According to the invention preferred are cationic surfactants of the quaternary ammonium type, the esterquats and the amidoamines. Preferred quaternary Ammonium compounds are ammonium halides, especially chlorides and bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® 180 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances which is under the name Tegoamid ^® S18 commercially available stearamidopropyl dimethylamine.

Next or instead of the cationic surfactants, the agents may be further Surfactants or emulsifiers, where in principle both anionic as well as ampholytic and nonionic surfactants and all types of known Emulsifiers are suitable. The group of ampholytic or too Amphoteric surfactants include zwitterionic surfactants and ampholytes. The surfactants may already have emulsifying effect.

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 1 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrestendgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 1 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol-Typen (Cognis),
• – alkoxilierte Triglyceride,
• – alkoxilierte Fettsäurealkylester der Formel (E4-I) R²²CO-(OCH₂CHR²³)_wOR²⁴ (E4-I)in der R²²CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R²³ für Wasserstoff oder Methyl, R²⁴ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Zuckertenside vom Typ der Alkyl- und Alkenyloligoglykoside gemäß Formel (E4-II), R²⁵O-[G]_p (E4-II)in der R²⁵ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Die Alkyl- und Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise von Glucose, ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (E4-II) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p im einzelnen Molekül stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R²⁵ kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C₈-C₁₀ (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C₈-C₁₈-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C₁₂-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C_9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R²⁵ kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C_12/14-Kokosalkohol mit einem DP von 1 bis 3.
• – Zuckertenside vom Typ der Fettsäure-N-alkylpolyhydroxyalkylamide, ein nichtionisches Tensid der Formel (E4-III),
  
  in der R²⁶CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²⁷ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpolyhydroxyalkylamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (E4-IV) wiedergegeben werden: R²⁸CO-NR²⁹-CH₂-(CHOH)₄CH₂OH (E4-IV)

Ampholytes are understood as meaning those surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytes are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• - Addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - With a methyl or C ₂ -C ₆ -Alkylrestendgruppenverschlossene addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide with linear and branched fatty alcohols having 8 to 30 C-Ato men, onto fatty acids having 8 to 30 carbon atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),
• - alkoxylated triglycerides,
• Alkoxylated fatty acid alkyl esters of the formula (E4-I) R ²² CO- (OCH ₂ CHR ²³ ) _w OR ²⁴ (E4-I) in R ²² CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{23 is} hydrogen or methyl, R ^{24 is} linear or branched alkyl radicals having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II), R ²⁵ O- [G] _p (E4-II) in which R ^{25 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in the individual molecule must always be integer and here before For all given values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ²⁵ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ²⁵ can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.
• Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III),
  
  R ^{26 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{27 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. At the fatty acid Re-N-alkylpolyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV): R ²⁸ CO-NR ²⁹ -CH ₂ - (CHOH) ₄ CH ₂ OH (E4-IV)

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{29 is} hydrogen or an alkyl group and R ²⁸ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or technical mixtures of these acids. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

When preferred nonionic surfactants are the alkylene oxide addition products saturated linear fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Agents with excellent properties are also obtained when used as nonionic surfactants fatty acid esters of ethoxylated Contain glycerol.

These Connections are identified by the following parameters. The alkyl radical contains 6 to 22 carbon atoms and can be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such Examples of alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-Lauryl, 1-myristyl. When using so-called "oxo-alcohols" as Starting materials predominate compounds with an odd Number of carbon atoms in the alkyl chain.

Farther may contain the sugar surfactants as nonionic surfactants be. In the compounds used as surfactant with alkyl groups they can each be uniform substances. It is however, usually preferred in the preparation of these substances to start from native plant or animal raw materials, so that you mix substances with different, from the respective Raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution thereby understood mixtures of homologues, which in the implementation of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrow homolog distributions are opposed obtained, for example, when hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or -alkoholate be used as catalysts. The usage of products with restricted homolog distribution may be preferred be.

The Amount of surfactant in the inventive textile or Surface treatment agent is highly dependent on the intended Application and is preferably in a range of 0.1 to 50% by weight, more preferably in a range of 0.5 to 25 wt .-% and most preferably in a range of 1 to 10 wt .-%, each based on the total amount of n means.

Farther can the textile or surface treatment agent of present invention at least one fragrance, the the agent preferably a pleasant and / or fresh fragrance impression gives. The at least one fragrance is not limited subjected. So can as at least one perfume individual Fragrance compounds, both synthetic or natural Compounds of the ester type, ethers, aldehydes, ketones, alcohols, Hydrocarbons, acids, carbonates, aromatic hydrocarbons, aliphatic hydrocarbons, saturated and / or unsaturated hydrocarbons and mixtures thereof.

When Duftaldehyde or Duftketone can all usual Fragrance aldehydes and fragrance ketones are used, which are typically used to bring about a pleasant scent sensation become. Suitable fragrance aldehydes and fragrance ketones are those skilled in the art well known.

The Proportion of the at least one perfume in the inventive Textile or surface treatment agent is preferably between 0.01 and 5 wt .-%, particularly preferably between 0.1 and 3 wt .-% and most preferably between 0.5 and 2 wt .-% based on the total amount of the agent.

Prefers are mixtures of different fragrances (from the different above-mentioned fragrance classes), which together have an appealing Create a fragrance. In this case, the total amount of at least a fragrance the amount of all the fragrances in the mix together based on the total amount of the agent.

In a preferred embodiment of the present invention it is the textile or surface treatment agent to a textile treatment agent, for example, for textile pretreatment as also used for textile aftertreatment and textile washing can be. The textile treatment agent can be used both in private Area as well as in the textile industry are used, whereby the nanoparticles according to the invention both to permanent as well as for temporary textile treatment can be.

In a highly preferred embodiment of Invention, said textile treatment agent is a detergent, Fabric softener, softening detergent or laundry detergent, wherein said agents in addition to the ingredients already mentioned other ingredients, such as builders, bleach, Bleach activators, enzymes, electrolytes, non-aqueous Solvent, pH adjuster, perfume carrier, Fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial Active ingredients, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, Repellents and impregnating agents, swelling and anti-sticking agents, neutral filler salts and UV absorbers may contain.

One Another object of the present invention is an adhesive, Sealant or coating agent comprising at least one curable Resin component and the nanoparticles according to the invention.

Of the Proportion of the nanoparticles according to the invention the respective adhesive, sealant or coating agent depending on the application, preferably between 0.1 and 25 wt .-%, more preferably between 0.5 and 15% by weight and most especially preferably between 1 and 10 wt .-%, each based on the total amount of the respective adhesive, sealant or coating agent.

Of the Proportion of the at least one curable resin component the respective adhesive, sealant or coating agent depending on the application, preferably between 50 and 95 wt .-%, more preferably between 60 and 90% by weight and more particularly preferably between 70 and 80 wt .-%, each based on the total amount of the adhesive, sealant or coating agent.

The curable resin component of the present invention selected from all monomers, oligomers or polymers, after curing in the inventive Means the desired bonding, sealing and / or cause coating effect. As at least one curable Resin component in the context of the present invention are preferably Resins selected from polyester, polyacrylate, polyurethane, Polyamide, polylactone, polycarbonate, and / or epoxy resins or Used silicones.

Also preferred are curable resin components which are any Mixture of two or more of said resins.

The Curing of the curable resin component takes place for example, thermally, by radiation and / or by the addition a hardener, the hardening method and the Curing conditions on the respective resin system and the appropriate application is to be agreed.

The compositions according to the invention can be formulated, on the one hand, as one-component adhesives, sealants or coating compositions, these being suitable both as highly viscous adhesives which can be applied warmly, sealing can be formulated as materials or as thermally or radiation-induced curable adhesives, sealants or coating compositions.

The On the other hand, agents of the invention can exist in two components, wherein a component A from a or more curable resin components or these contains and a second component B of one or more Hardeners for the curable resin component exists or contains. As a hardener in the Component B can be used compounds that opposite the at least one curable resin component have reactive groups.

there can the nanoparticles according to the invention in component A, component B or in both components available. Preferably, the inventive Nanoparticles in component A included.

there it is possible the component A, comprising the inventive Nanoparticles and the at least one curable resin component at elevated temperatures, such as at temperatures of 40 to 120 ° C over a period of 1 min to 12 h pretreat.

By the thermal pretreatment becomes a very homogeneous, against sedimentation or agglomeration extremely long-term stable component A received. Due to the temperature and length of the thermal Pretreatment can continue the crosslinking and viscosity be controlled the said component.

at The formulation as a two-component agent becomes the two reaction components just before the application mixed together, with the curing then at room temperature or moderately elevated Temperature takes place. As the second reaction component B can b the two-component epoxy resin-based adhesives known reaction components used as a hardener be such as di- or polyamines.

These it is the agent of the invention to a Adhesive, so it is particularly advantageous if the at least a resin component is an epoxy resin or a mixture of various ones Epoxy resins includes.

Under an "epoxy resin" is used in the present Invention understood a resin composition based on formed by epoxy compounds or epoxide-containing compounds is, these compounds preferably at least two epoxy groups include.

In a preferred embodiment of the invention can the epoxy compounds or epoxide-containing compounds of the epoxy resin system the polymerizable preparation both oligomeric and monomeric Epoxy compounds and polymeric-type epoxies include and may be aliphatic, cycloaliphatic, aromatic or represent heterocyclic compounds.

suitable Epoxy resins in the context of the present invention are, for example preferably selected from bisphenol A type epoxy resins, Bisphenol-S type epoxy resins, bisphenol F type epoxy resins, Phenolic novolac type epoxy resins, cresol novolac type epoxy resins, epoxidized products of numerous dicyclopentadiene-modified Phenolic resins, obtainable by reaction of dicyclopentadiene with numerous phenols, epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, aromatic epoxy resins such as epoxy resins with naphthalene skeleton and epoxy resins with fluorene skeleton, aliphatic epoxy resins such as neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate, and epoxy resins having a hetero ring such as triglycidyl isocyanurate.

Especially For example, the epoxy resins include the reaction product of bisphenol A and epichlorohydrin, the reaction product of phenol and formaldehyde (Novolak resins) and epichlorohydrin, glycidyl esters and the reaction product from epichlorohydrin and p-aminophenol.

Further Polyphenols obtained by reaction with epichlorohydrin (or epibromohydrin) suitable epoxy resin prepolymers are: resorcinol, 1,2-dihydroxybenzene, Hydroquinone, bis (4-hydroxyphenyl) -1,1-isobutane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane and 1,5-hydroxynaphthalene.

Other preferred epoxy resins that are commercially available include, in particular, octadecylene oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ether of Bisphenol A (for example, those sold under the trade designations "Epon 828", "Epon 825", "Epon 1004" and "Epon 1010" by Hexion Specialty Chemicals Inc., "DER-331", "DER-332"). , "DER-334", "DER-732" and "DER-736" available from Dow Chemical Co.), vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate, 3,4-epoxy-6 methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexene carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, aliphatic polypropylene glycol modified epoxide, dipentene dioxide, epoxidized polybutadiene (e.g. B. Krasol products of Sartomer), epoxy resin-containing silicone resin, flame-retardant epoxy resins (e.g., "DER-580", a bisphenol-type brominated epoxy resin available from Dow Chemical Co.), 1,4-butanediol diglycidyl ethers of a phenol-formaldehyde novolak (e.g., "DEN-431" and "DEN-438" of Dow Chemical Co.), as well as resorcinol diglyc idyl ether (e.g., "Kopoxite" from Koppers Company Inc.), bis (3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta dioxane, vinylcyclohexene monoxide, 1,2-epoxyhexadecane, alkyl glycidyl ethers such as. C8-C10 alkyl glycidyl ethers (eg "HELOXY Modifier 7" from Hexion Specialty Chemicals Inc.), C12-C14 alkyl glycidyl ethers (eg "HELOXY Modifier 8" from Hexion Specialty Chemicals Inc.), butyl glycidyl ether ( for example, "HELOXY Modifier 61" from Hexion Specialty Chemicals Inc.), cresyl glycidyl ether (eg, "HELOXY Modifier 62" from Hexion Specialty Chemicals Inc.), p-tert-butylphenyl glycidyl ether (e.g. HELOXY Modifier 65 "from Hexion Specialty Chemicals Inc.), polyfunctional glycidyl ethers such as. Diglycidyl ether of 1,4-butanediol (e.g., "HELOXY Modifier 67" from Hexion Specialty Chemicals Inc.), diglycidyl ether of neopentyl glycol (e.g., "HELOXY Modifier 68" from Hexion Specialty Chemicals Inc.), diglycidyl ether from Cyclohexanedimethanol (e.g., "HELOXY Modifier 107" from Hexion Specialty Chemicals Inc.), trimethylolethane triglycidyl ether (e.g., "HELOXY Modifier 44" from Hexion Specialty Chemicals Inc.), trimethylolpropane tiglycidyl ether (e.g., "HELOXY Modifier 48 "from Hexion Specialty Chemicals Inc.), polyglycidyl ethers of an aliphatic polyol (e.g.," HELOXY Modifier 84 "from Hexion Specialty Chemicals Inc.), polyglycol diepoxide (e.g.," HELOXY Modifier 32 "from Hexion Specialty Chemicals Inc.). ), Bisphenol F epoxides (e.g., "EPN-1138" or GY-281 "from Huntsman Int. LLC), 9,9-bis-4- (2,3-epoxypropoxy) -phenylfluorenone (e.g. "Epon 1079" from Hexion Specialty Chemicals Inc.).

Further preferred commercially available compounds are, for. Selected from Araldite ^™ 6010, Araldit ^™ GY-281 ^™ , Araldit ^™ ECN-1273, Araldit ^™ ECN-1280, Araldit ^™ MY-720, RD-2, available from Huntsman Int. LLC; DEN ^TM 432, ^TM 438, ^TM 485 from Dow Chemical Co., Epon ^™ 812, 826, 830, 834, 836, 871, 872, 1001, 1031 etc. from Hexion Specialty Chemicals Inc. and HPT ^™ 1071, HPT ^TM 1079 also from Hexion Specialty Chemicals Inc., as novolac resins further, for example, Epi-Rez ^™ 5132 from Hexion Specialty Chemicals Inc., ESCN-001 from Sumitomo Chemical, Quatrex 5010 from Dow Chemical Co., RE 305S from Nippon Kayaku, Epiclon ^TM N673 from DaiNipon Ink Chemistry or Epicote ^™ 152 from Hexion Specialty Chemicals Inc ..

For certain applications, it may be advantageous thermally activated or to use latent hardeners.

When thermally activated or latent hardener for Epoxy resins can, for example, guanidines, substituted Guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and / or their Mixtures are used. The hardeners can both stoichiometrically in the curing reaction However, they can also be catalytically active be.

Examples substituted guanidines are methylguanidine, dimethylguanidine, Trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, Tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine and cyanoguanidine. Examples of suitable melamine resins are methoxymethyl-methylolmelamine, hexamethoxymethylmelamine, methoxymethylmelamine, Hexamethoxymethylmelamine. As a representative of suitable guanamine derivatives are alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxymethyl-benzoguanamine called.

When Examples of aromatic amines are aromatic diamines, such as 4,4'-diaminodiphenylsulfone, 4,4'-methylenedianiline, m-phenylenediamine called.

For the one-component, thermosetting adhesives of course the selection criterion is the low solubility of these substances at room temperature in the at least one resin component. In addition to or instead of the aforementioned hardeners, catalytically active substituted ureas can be used. These are in particular the p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (Fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron). In principle, it is also possible to use catalytically active tertiary acrylic or alkyl amines, for example the benzyldimethylamine, tris (dimethylamino) phenol, piperidine or piperidine derivatives. Furthermore, various, preferably solid, Imidazole derivatives are used as catalytically active accelerator. It is also possible to use combinations of hardener and accelerator.

adhesives of the present invention include besides the invention Nanoparticles particularly preferably bisphenol A and / or bisphenol F based epoxy resins as at least one curable resin component and at least one hardener, this preferably is selected from aromatic diamines such. B. 4,4'-diaminodiphenylsulfone.

In usually contain adhesives in addition to the components already described furthermore known per se colorants and / or fillers such for example the various ground or precipitated crayons, Carbon black, calcium magnesium carbonates, barite and in particular silicatic fillers of the aluminum-magnesium-calcium silicate type, z. B. wollastonite, chlorite.

Farther the adhesives can be common other auxiliary and Additives such. As plasticizers, reactive diluents, rheology aids, Wetting agents, anti-aging agents, stabilizers and / or color pigments included. Preferably, however, the adhesives are free of plasticizers. When Rheology aids may, for. Fumed silicas, Bentone or fibrillated or pulp short fibers in the range between 0.1 and 5% are added.

Reactive diluents for the purposes of this invention are epoxide-containing, low-viscosity substances (glycidyl ethers or glycidyl esters) having an aliphatic or aromatic structure. These reactive diluents serve on the one hand to reduce the viscosity of the binder system above the softening point, on the other hand they control the pre-gelation process by injection molding. Typical examples of reactive diluents to be used according to the invention are mono-, di- or triglycidyl ethers of C ₆ - to C ₁₄ -monoalcohols or alkylphenols and the monoglycidyl ethers of cashew nut shell oil, diglycidyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1 , 4-butylene glycols, 1,5-pentanediols, 1,6-hexanediols, cyclohexanedimethanols, triglycidyl ethers of trimethylolpropane and the glycidyl esters of C ₆ - to C ₂₄ -carboxylic acids or mixtures thereof.

Farther For example, the present invention includes an article that is at least contains a component with a Adhesive, sealant or coating agent glued, sealed, or is coated. The at least one component may be one or more metal components, in particular metal sheets act, which formed into hollow bodies and joined could be. In particular, the object may be a vehicle represent.

After all For example, the present invention includes a method of impact modification and / or for improving the tensile shear strength of an adhesive, wherein the adhesive before curing with the inventive Nanoparticles is added.

Should the adhesive is a 2-component adhesive, so can be made in accordance with the above Statements the resin component and / or the hardener component mixed with the nanoparticles according to the invention become.

embodiments

1. Preparation of the invention nanoparticles

1.1 Epoxy Functionalization of the Nanoparticular Silica cores

Starting materials:

• - DOWEX HCR-W2, ion exchanger (Dow, Merck).
• - Nanoparticulate silica cores Bindzil 30NH _3/220, spec. Surface area: 220 m ² / g, Akzo-Nobel, d = 1.2 g / cm ³
• - isopropanol, 99.5%
• 3-glycidoxypropyltrimethoxysilane (GLYMO), GE Silicones, Silquest A-187

execution

450 g DOWEX HCR-W2 are placed in a beaker. While stirring, 110 ml of the aqueous Bindzil dispersion are added within 15 min. It is stirred for 15 min and then the ion exchanger is filtered off.

87.56 g isopropanol and 87.56 g of the pretreated Bindzil dispersion are placed in a 500 ml round bottom flask and stirred heated to 60 ° C. Within 2 hours 17.51 g of 3-glycidoxypropyltrimethoxysilane was added and the reaction solution then stirred for 2 h at 60 ° C.

you obtains a clear, low-viscous dispersion of epoxy-functionalized, nanoparticulate silica cores.

1.2 Implementation of the epoxy-functionalized Silica cores with polyoxyalkylene monoamines

Obtained in Example 1.1 low-viscous dispersion of epoxy-functionalized, nanoparticulate silica cores is mixed with 148.0 g of Polyoxyalkylenmonoamis Jeffamine ^® M-2070 (Messrs. Huntsman) and then stirred at 20 ° C for 20 hours. After removal of the solvent gives a yellowish, highly viscous substance which can be easily redispersed both in water and isopropanol.

TEM (Transmission Electron Microscopy) of the nanoparticles obtained, that substantially spherical particles with a middle Particle diameters of 10 to 80 nm were obtained.

2. washing tests

The nanoparticles prepared according to Example 1.2 were in an amount of 2 wt .-% in an otherwise usual mixed liquid detergent mixed, the in addition to water, also 20.1% by weight of surfactants, 0.75% by weight Enzyme mixture (protease / amylase), 1.0% by weight boric acid, 2.1 % By weight of citric acid, 6.0% by weight of propylene glycol, 0.2% by weight Diethylenetriaminepenta-methylenephosphonic acid and 3.1% by weight Sodium hydroxide contained.

For comparison, a reference detergent was prepared that was otherwise the same but did not contain the nanoparticles. To determine the detergency, white cotton fabrics were contaminated with standardized test stains (A: lipstick L'Oreal 453, B: skin fat) and then the respective Y values were determined ( _Yvorter ). Thereafter, the cotton fabric at 40 ° C was added (120 g of detergent, water hardness 16 ° d, load 3.5 kg standard program) washed in a domestic washing machine (Miele Novotronic ^® W 918). The fabrics were dried and the Y-values (Y _after ) were again determined for the dried fabrics. The Y values were determined in all cases with a Minolta CR 200. The resulting wash results (ΔY values) given in Table 1 were obtained. Table 1: Wash results soiling Reference detergent [ΔY] Detergent + 2% by weight of nanoparticles [ΔY] A 28.2 36.9 B 46.8 53.5 LV = Y _after - Y _before

The Results shown in Table 1 demonstrate that the washing performance a conventional detergent by the addition of the invention Nanoparticles in relation to the examined test stains clearly is improved.

3. Adhesives

3.1 1-Component Adhesive A

Using a speed mixer, a 1-component adhesive (Adhesive A) was obtained by mixing the following ingredients: Composition of Adhesive A (1% by weight of nanoparticles) raw material product Quantity [g] epoxy resin Epikote 828, 10 Hardener (DDS) 4'4'diaminodiphenyl sulfone, Merck 3 nanoparticles Product from example 1.2 0,448

3.2 1-component adhesive B

With the help of a speed mixer, a 1-component adhesive (adhesive B) was obtained by mixing the following components: Composition Adhesive B (2% by weight of nanoparticles) raw material product Quantity [g] epoxy resin Epikote 828, 10 Hardener (DDS) 4'4'diaminodiphenyl sulfone, Merck 3 nanosilica Product from example 1.2 0.928

3.3 1-Component Comparative Adhesive C

With the aid of a speed mixer, a 1-component comparison adhesive (adhesive C) was obtained by mixing the following ingredients: Composition Adhesive C (0 wt .-% nanoparticles) raw material product Quantity [g] epoxy resin Epikote 828, 10 Hardener (DDS) 4'4'diaminodiphenyl sulfone, Merck 3

3.4 1-Component Adhesive D

With the help of a speed mixer, a 1-component adhesive (Adhesive D) was obtained by mixing the following components: Composition Adhesive D (1.5% by weight of nanoparticles) raw material product Quantity [g] epoxy resin Epikote 828, 10 Hardener (DDS) 4'4'diaminodiphenyl sulfone, Merck 3 nanosilica Product from example 1.2 0.684

3.5 Determination of tensile shear strength

Execution:

It in each case three steel test specimen pairs were Way glued: The steel specimens were initially using methyl ethyl ketone for 5 minutes in the ultrasonic bath cleaned and then again with ethanol in the range the adhesive surface cleaned. The Schicktdicke was with Glass beads and adjusted to about 0.2 mm using an adhesive device. After applying the adhesive to a surface of about 10 × 20 mm with 1 mm thick steel and 10 × 25 mm with 2 mm thick steel and the removal of excess Adhesive residues were fixed to the specimens and for 2 h at 130 ° C and 2 h at 170 ° C and then again for 2 h at 190 ° C. cured in an oven. After a cooling time from approx.

12 h, the tensile shear strength of the adhesive bond mechanically with a Tensile testing machine Zwick Z010 at a test speed of 10 mm / min determined.

Results:

With freshly prepared adhesives, the following tensile shear strengths were determined: steel thickness Adhesive C (Ref.) Adhesive A Adhesive B 1 mm steel 11.9 MPa 15.0 MPa 13.6 MPa 2 mm steel 15.2 MPa 15.5 MPa 18.9 MPa

With 7 days of aged adhesives, the following tensile shear strengths were determined: steel thickness Adhesive C (Ref.) Adhesive A Adhesive B Adhesive D 2 mm steel 0 MPa * 15.8 MPa 15.1 MPa 16.0 MPa * Glue very brittle and glassy

By the addition of nanoparticles according to the invention can determine the tensile shear strengths of the investigated epoxy-based Adhesives and their aging resistance significantly be improved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 2006/01680 A1 [0003]
• WO 2003/047753 A1 [0004]
• US 2007/0275042 A1 [0007]
• US 2008/0021147 A1 [0008]
• US 2631134 [0031]

Cited non-patent literature

• - N. Joubert, C. Delaite, E. Bourgeat-Lami and P. Dumas (Macromol Rapid Commun. 2005, 602-607) [0005]
• - Fujiki et al. (Journal of Macromolecular Science Part A, 2000, 34 (4) 357-377) [0006]
• W. Stöber et al. in J. Colloid and Interface Science 26, 62 (1968) and 30, 568 (1969) [0030]
• - H. Schmidt, Chemistry in Our Time, 35 (3) 176-184 (2001) [0030]

Claims (15)

Nanoparticles, containing a) Cores from one inorganic material, b) at least one silane group comprising Interlayer and c) at least one polyoxyalkylene monoamine comprehensive outer layer. Nanoparticles according to claim 1, characterized in that that they have a mean particle diameter of 15 nm to 250 nm exhibit. Nanoparticles according to one or both of the claims 1 and 2, characterized in that the inorganic material the cores a) is selected from oxides or hydroxides of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium, Zirconium and / or aluminum. Nanoparticles according to at least one of the claims 1 to 3, characterized in that the polyoxyalkylene monoamines the outer layer via their amino groups are covalently bound to the silane groups of the intermediate layer, wherein each silane group has at least one hydroxyl group, which are covalently linked to a carbon atom of the silane group is. Nanoparticles according to at least one of claims 1 to 4, characterized in that the intermediate layer comprising at least one silane group at least one structural unit selected from structural units of the formula (Ia),

of the formula (Ib),

and / or the formula (Ic),

wherein R ¹ and R ² independently represent a linear or branched optionally substituted C 1-12 alkyl group, a linear or branched optionally substituted C 1-12 alkoxy group, an optionally substituted C 6-12 aryl group, an optionally substituted C 6-12 cycloalkyl group or an optionally substituted C8-12 aralkyl group, R ^3, R ⁴ and R ^{5 are} independently hydrogen or an optionally substituted C1-12 alkyl, C3-8 cycloalkyl, C2-5 alkenyl, C2-6 alkynyl-C1 R ^{3 'is} hydrogen, halogen or an optionally substituted C 1-12 alkyl or C 1-12 alkoxy group and Y is an optionally substituted C 6-12 alkoxyalkyl group, R ^{2' is} heterocyclic, C 2-8 heterocycloalkyl or C 2-12 alkoxyalkyl; an optionally substituted C8-12 aralkylene group, a C5-12 optionally substituted cycloalkylene group, or a linear or branched chain optionally substituted C1-18 alkylene group, wherein the carbon chain of the alkylene group may be interrupted by non-adjacent oxygen or sulfur groups. Nanoparticles according to at least one of the claims 1 to 5, characterized in that the polyoxyalkylene monoamines the outer layer of ethylene oxide and / or propylene oxide units include. Nanoparticles according to at least one of the claims 1 to 6, characterized in that the amino group of the polyoxyalkylene monoamines is a primary amino group. Nanoparticles according to at least one of the claims 1 to 7, characterized in that the polyoxyalkylaminoamines the outer layer has a weight average molecular weight from 500 g / mol to 10,000 g / mol. Textile or surface treatment agents, full a) at least one surfactant and b) nanoparticles according to one of claims 1 to 8. Adhesive, sealant or coating agent, full a) at least one curable resin component and b) nanoparticles according to one of the claims 1 to 8. Object containing at least one component, with an adhesive, sealant or coating agent Claim 10 glued, sealed, or coated. Process for the preparation of nanoparticles according to of claims 1 to 8, comprising the steps: a) Provision of nanoparticulate cores from an inorganic Material, b) Surface functionalization of the nanoparticulate Cores with epoxy groups by reaction of said cores with at least an epoxy silane and c) reaction of the product obtained in step b) Epoxy-functionalized cores having at least one polyoxyalkylene monoamine, which only one to the epoxy groups of the epoxy-functionalized Cores having reactive functional group. A method according to claim 12, characterized in that the at least one epoxy silane is selected from compounds of general formula E- (I)

and / or from compounds of the general formula E- (II),

wherein R ^{9 is} a linear or branched optionally substituted C 1-4 alkyl group or an optionally substituted C 6-12 aryl group, R ^{9 is} a linear or branched optionally substituted C 1-6 alkyl group, u is 0, 1 or 2 and k is a integer from 1 to 5 stands. Process for impact modification and / or to improve the tensile shear strength of an adhesive, thereby characterized in that the adhesive before curing with Nanoparticles according to one of the claims 1 to 8 is offset. Use of the nanoparticles according to a of claims 1 to 8 for improving the soil release of and / or reduction of re-fouling on textile or hard surfaces.