DE10200928A1 - Organic dispersions of surface-modified nanoparticles, processes for their production and their use - Google Patents

Abstract

Organic dispersions of surface-modified nanoparticles, can be produced by using DOLLAR A (1) a mixture containing DOLLAR A (A) nanoparticles, DOLLAR A (B) an amphiphile and DOLLAR A (C) a compound with at least two groups with actinic radiation, DOLLAR A is subjected to a strong shear, after which the mixture (1) DOLLAR A (2) together with a mixture containing DOLLAR A (D) is a compound of the general formula I: DOLLAR A (S¶o¶L-) ¶m¶M (R) ¶n¶ (H) ¶p¶ (II), DOLLAR A where the indices and the variables have the following meaning: DOLLAR AS reactive functional group; DOLLAR A L at least two-membered linking group; DOLLAR A H hydrolyzable group or atom; DOLLAR A M two- to six-valent main group and sub group metal; DOLLAR A R organic group; DOLLAR A o integer from 1 to 5; DOLLAR A m + n + p integer from 2 to 6; DOLLAR A p integer from 1 to 6 DOLLAR A m and n zero or integer from 1 to 5; and DOLLAR A (E) subjects DOLLAR A to low shear; Process for their preparation and their use.

Description

The present invention relates to new organic dispersions of surface modified nanoparticles. In addition, the present concerns Invention a new process for the production of organic dispersions of surface modified nanoparticles. In addition, the present concerns Invention the use of the new organic dispersions from surface modified nanoparticles as coating materials, adhesives and Sealants or for their manufacture and for the manufacture of Moldings, in particular optical moldings, and self-supporting films.

Organic dispersions of surface-modified nanoparticles are known.

So go from the American patent US 4,652,479 A organic Dispersions of surface-modified nanoparticles that are produced by Grinding of silicon dioxide nanoparticles can be produced in monoalcohols. The contained in the known organic dispersions However, surface-modified nanoparticles have no reactive functional ones Groups on.

From the German patent application DE 195 40 623 A1 are organic Dispersions of surface-modified nanoparticles known for example made from boehmite and 3-methacryloyloxypropyltrimethoxysilane become. The resulting sol is diluted with 2-isopropoxyethanol, whereupon the addition of triethylene glycol dimethacrylate follows. There is a grinding process not provided The organic dispersions are used as coating materials used and radically hardened with peroxides.

From European patent application EP 0 832 947 A2 are organic Dispersions of surface-modified nanoparticles known for example from colloidal silicon dioxide and the reaction product of 3- Isocyanatopropyltrimethoxysilan and hydroxypropyl carbamate can be produced. A grinding process is not provided. The dispersions are in solvent-based, thermally curable clear coats based on binders containing carbamate groups are used.

European patent application EP 0 872 500 A1 describes organic ones Dispersions of surface-modified nanoparticles known for example from colloidal metal oxides and the reaction products of with 3,5-dimethylpyrazole partially blocked hexamethylene diisocyanate and N- (3- Trimethoxysilylpropyl) -aspartic acid diethyl ester in isopropanol / water getting produced. Isopropanol is then added by vacuum distillation 40 ° C removed and replaced by a higher boiling solvent. A grinding process is not scheduled. The dispersions are used for the production of thermal curable coating materials based on polyesters.

From the German patent application DE 197 19 948 A1 are organic Dispersions of surface-modified nanoparticles known for example made of silicon dioxide, which is stirred and ultrasound in the Isopropanol was dispersed, and 3-methacryloyloxypropyltrimethoxysilane getting produced. The resulting dispersion is with Tetraethylene glycol dimethacrylate and a photoinitiator. On Grinding is not planned. The solvent is then removed in vacuo partially distilled off. The mixture is used to produce molded articles. To for this purpose it is poured into a mold and exposed to UV radiation and IR Radiation hardened. The result is a solvent-free, binder-containing Silicon dioxide molded body, which corresponds to a ceramic green body. This is fully fired at temperatures from 500 to 1,400 ° C.

International patent application WO 00/22039 describes organic Dispersions of surface-modified nanoparticles known for example, by implementing silicon dioxide nanoparticles with 3- Methacryloyloxypropyltrimethoxysilane and aluminum triisopropylate in ethoxylated Pentaerythritol tetraacrylate can be produced at 80 ° C. After its manufacture the mixture is brought to room temperature as quickly as possible Coating processing cooled. A grinding process is not provided. The The coating material is cured using electron beams.

From the international patent application WO 00/22052 are further organic Dispersions of surface-modified nanoparticles known for example by adding silicon dioxide nanoparticles and 3- Methacryloyloxypropyltrimethoxysilane in bisethoxy-bisphenol-A-diacrylate, dissolved in Tripropylene glycol diacrylate, can be produced at 80 ° C. The resulting one Dispersion is used to produce coatings and is used with Hardened electron radiation.

From the VILF series of lectures by the Association of Engineers in Paint and Farbenfachs e. V., Volume 3, S. Frahn, V. Valter, T. Ladwig, M. Ettinger and J. Meyer, "New modified, highly disperse silicon dioxide for radiation curing Lacquer systems ", pages 89 to 89, are curable with actinic radiation Coating materials (100% systems) known, which with 3- Methacryloxypropyltrimethoxysilane modified nanoparticles based on Silicon dioxide in an amount of 5 to 16% by weight and polyester acrylates, Oligoether acrylates, urethane acrylates, ethoxylated pentaerythritol tetraacrylate or Epoxy acrylate and a photoinitiator included. Incorporation of the surface modified nanoparticles into the olefinically unsaturated Connections were made by pre-dispersing the surface modified Nanoparticles in a dissolver and grinding the resulting Coating material with a bead mill, so that the grindometer value is below 10 µm lies. It is not clear from the article under what conditions the surface of the nanoparticles was modified.

When modifying the surface of nanoparticles with, for example, 3- Methacryloyloxypropyltrimethoxysilane, triethoxysilane or tri-sec.-butoxysilane in the presence of higher functional olefinically unsaturated monomers Temperatures at which the alcohol formed distills off occur Transesterification between the acrylate monomers and the alcohol, resulting in a considerable odor nuisance due to methyl acrylate, ethyl acrylate or sec. Butyl acrylate is formed.

In addition, the known organic dispersions of Surface-modified nanoparticles are often difficult to find in coating materials incorporate because there are compatibility problems. These lead to one inhomogeneous distribution of the surface modified nanoparticles in the Coating materials, which can be seen in the coatings produced from them or optical moldings through cloudiness. Such However, cloudiness is particularly evident in clearcoats and optical moldings extremely undesirable and disadvantageous.

In order to solve the compatibility problem, the international Patent application WO 00/75244 proposed to contain glycidyl groups Implement binders with carboxyl-functional nanoparticles. this happens for example by the copolymerization of epoxy groups Monomers and monomers free of epoxy groups in the presence of carboxyl functional nanoparticles. But this solution is comparative complex because it is not possible to determine the material composition of Varying coating materials by using commercially available Coating materials combined with surface-modified nanoparticles, you have to make a special one with nanoparticles for each individual case Produce a modified binder. One is also concerned with the use of carboxy-functional nanoparticles bound.

Since the known organic dispersions of surface modified Nanoparticles, especially those with actinic radiation or thermal and with actinic radiation curable dispersions, valuable starting materials for the Production of highly scratch-resistant coatings, optical moldings or cantilever films, it is highly desirable to manufacture them to improve and simplify.

Since surface-modified nanoparticles increase the scratch resistance of coatings, those from usual and known, thermal and with actinic radiation curable coating materials are produced, significantly improve it also highly desirable to incorporate the surface-modified nanoparticles in these coating materials improve.

Here and in the following is electromagnetic under actinic radiation Radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, especially UV radiation, or corpuscular radiation, such as Electron radiation to understand. The common hardening of Coating materials, adhesives and sealants with heat and actinic Radiation is also called dual-cure by experts.

In the unpublished German patent application DE 101 26 651.0 thermally or thermally and curable with actinic radiation Known coating materials containing surface-modified nanoparticles, as from the VILF-lectures by the Association of Engineers of the Lack- und Farbenfachs e. V., Volume 3, S. Frahn, V. Valter, T. Ladwig, M. Ettinger and J. Meyer, "New Modified Highly Dispersed Silicas for radiation-curing lacquer systems "are known. These surface-modified Nanoparticles are preferably in the form of a coating material Paste added. The paste is prepared by pre-dispersing the surface modified nanoparticles in a binder solution and grinding of the dispersion. The coating materials can be even more functional contain olefinically unsaturated monomers, such as dipentaerythritol pentaacrylate, which but not about the organic dispersion of the surface modified Nanoparticles, but are entered separately.

The object of the present invention is to develop new organic dispersions of To provide surface modified nanoparticles that have the disadvantages of No longer have the state of the art, but rather in simpler Have it made without causing any unpleasant odors unwanted by-products comes.

In addition, the new organic dispersions surface modified nanoparticles as coating materials, adhesives and Sealants are suitable.

Furthermore, the new organic dispersions should surface-modified nanoparticles for the production of moldings, in particular optical moldings, and self-supporting films are suitable.

In particular, the new organic dispersions should surface-modified nanoparticles in conventional and known, thermally and / or with actinic radiation, in particular thermally and coating materials, adhesives and curable with actinic radiation Allow sealing compounds to be distributed homogeneously, so that they are free of turbidity and are highly scratch-resistant Coatings, adhesive layers and seals, in particular clearcoats, result.

• 1. in einer ersten Stufe eine Mischung, enthaltend
  • A) Nanopartikel mindestens einer Art,
  • B) mindestens ein Amphiphil und
  • C) mindestens eine Verbindung mit mindestens zwei reaktiven funktionellen Gruppen, die mindestens eine mit aktinischer Strahlung aktivierbare Bindung enthalten,
  einer starken Scherung unterwirft, wonach man die resultierende Mischung (1)
• 2. in mindestens einer weiteren Stufe zusammen mit einer Mischung, enthaltend
  • A) mindestens eine Verbindung der allgemeinen Formel I:
    
    (S_oL-)_mM(R)_n(H)_p (I),
    
    worin die Indizes und die Variablen die folgende Bedeutung haben:
    S reaktive funktionelle Gruppe;
    L mindestens zweibindige, verknüpfende, organische Gruppe;
    H hydrolysierbare, einbindige, organische Gruppe oder hydrolysierbares Atom;
    M zwei- bis sechswertiges Hauptgruppen- und Nebengruppen- Metall;
    R nicht hydrolysierbare, einbindige, organische Gruppe;
    o eine ganze Zahl von 1 bis 5;
    m + n + p eine ganze Zahl von 2 bis 6;
    p eine ganze Zahl von 1 bis 6
    m und n Null oder eine ganze Zahl von 1 bis 5; und
  • B) Wasser
  einer schwachen Scherung unterwirft.

Accordingly, the new organic dispersions of surface-modified nanoparticles have been found which can be prepared by

• 1. in a first stage containing a mixture
  • A) nanoparticles of at least one type,
  • B) at least one amphiphile and
  • C) at least one compound with at least two reactive functional groups which contain at least one bond which can be activated with actinic radiation,
  subjected to strong shear, after which the resulting mixture (1)
• 2. in at least one further step together with a mixture containing
  • A) at least one compound of the general formula I:
    
    (S _o L-) _m M (R) _n (H) _p (I),
    
    where the indices and the variables have the following meaning:
    S reactive functional group;
    L at least double-bonded, linking organic group;
    H hydrolyzable, monovalent organic group or hydrolyzable atom;
    M bivalent to hexavalent main group and sub group metal;
    R non-hydrolyzable, single-membered organic group;
    an integer from 1 to 5;
    m + n + p is an integer from 2 to 6;
    p is an integer from 1 to 6
    m and n are zero or an integer from 1 to 5; and
  • B) water
  subject to weak shear.

The new organic dispersions of surface-modified nanoparticles as "dispersions according to the invention" designated.

• 1. in einer ersten Stufe eine Mischung, enthaltend
  • A) Nanopartikel mindestens einer Art,
  • B) mindestens ein Amphiphil und
  • C) mindestens eine Verbindung mit mindestens zwei reaktiven funktionellen Gruppen, die mindestens eine mit aktinischer Strahlung aktivierbare Bindung enthalten,
  bei Temperaturen ≤ 40°C einer starken Scherung unterwirft, wonach man die resultierende Mischung (1)
• 2. in mindestens einer weiteren Stufe zusammen mit einer Mischung, enthaltend
  • A) mindestens eine Verbindung der allgemeinen Formel I:
    
    (S_oL-)_mM(R)_n(H)_p (I),
    
    worin die Indizes und die Variablen die folgende Bedeutung haben:
    S reaktive funktionelle Gruppe;
    L mindestens zweibindige, verknüpfende, organische Gruppe;
    H hydrolysierbare, einbindige, organische Gruppe oder hydrolysierbares Atom;
    M zwei- bis sechswertiges Hauptgruppen- und Nebengruppen- Metall;
    R nicht hydrolysierbare, einbindige, organische Gruppe;
    o eine ganze Zahl von 1 bis 5;
    m + n + p eine ganze Zahl von 2 bis 6;
    p eine ganze Zahl von 1 bis 6
    m und n Null oder eine ganze Zahl von 1 bis 5; und
  • B) Wasser
  bei Temperaturen ≤ 40°C einer schwachen Scherung unterwirft.

In addition, the new process for the production of organic dispersions of surface-modified nanoparticles was found, in which

• 1. in a first stage containing a mixture
  • A) nanoparticles of at least one type,
  • B) at least one amphiphile and
  • C) at least one compound with at least two reactive functional groups which contain at least one bond which can be activated with actinic radiation,
  subjected to strong shear at temperatures ≤ 40 ° C, after which the resulting mixture (1)
• 2. in at least one further step together with a mixture containing
  • A) at least one compound of the general formula I:
    
    (S _o L-) _m M (R) _n (H) _p (I),
    
    where the indices and the variables have the following meaning:
    S reactive functional group;
    L at least double-bonded, linking organic group;
    H hydrolyzable, monovalent organic group or hydrolyzable atom;
    M bivalent to hexavalent main group and sub group metal;
    R non-hydrolyzable, single-membered organic group;
    an integer from 1 to 5;
    m + n + p is an integer from 2 to 6;
    p is an integer from 1 to 6
    m and n are zero or an integer from 1 to 5; and
  • B) water
  subject to weak shear at temperatures ≤ 40 ° C.

The following is the new process for the production of organic Dispersions of surface-modified nanoparticles as "according to the invention Procedure ".

Furthermore, the new coating materials, adhesives and Sealants found that have at least one according to the invention and / or at least one manufactured according to the inventive method Contain dispersion and the "inventive Coating materials, adhesives and sealants "are referred to.

Further subjects of the invention are evident from the description.

In view of the prior art, it was surprising and for the One skilled in the art could not have foreseen that the object of the present invention on the basis of the dispersions of the invention and the could be solved method according to the invention.

In particular, it was surprising that in the method according to the invention No more unpleasant odors caused by undesirable by-products. As a result, the dispersions of the invention were particularly good for Production of optical moldings and self-supporting foils suitable.

What was even more surprising was that they were free of unwanted smells Dispersions according to the invention readily homogeneous in known thermally and / or curable with active radiation, in particular thermally and curable with actinic radiation, coating materials, adhesives and Have sealants incorporated. The invention Coating materials, adhesives and sealants therefore supplied by Turbidity-free, highly scratch-resistant coatings, adhesives and seals, especially clear coats.

The dispersions according to the invention are according to the invention Process can be produced.

In the method according to the invention, in a first stage (1) Mixture containing nanoparticles (A) of at least one, in particular one, type, at least one amphiphile (B) and at least one compound (C) with at least one two reactive functional groups, at least one with actinic Contain radiation-activatable bond, subjected to strong shear.

The strong shear can be applied with conventional and known devices become. Examples of suitable devices are gear rim dispersers or Mills. Mills, in particular grinding media, are preferred Agitator mills and ball mills, used (cf. Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 369 and 370, "grinding media").

Step (1) is preferably carried out at a temperature of 40 40 ° C., preferably ≤ 30 ° C. and in particular carried out at room temperature.

The mixture (1) can be sheared for more or less long. Preferably the duration of the shear is 10 minutes to 10 hours, preferably 20 Minutes to 5 hours and especially 30 minutes to 3 hours.

• - 1 bis 10, bevorzugt 2 bis 8 und insbesondere 3 bis 7 Gew.% (A),
• - 10 bis 80, bevorzugt 15 bis 60 und insbesondere 20 bis 50 Gew.% (B) und
• - 19 bis 80, bevorzugt 38 bis 77 und insbesondere 47 bis 73 Gew.% (C).

enthalten. The composition of the mixture (1) can vary widely and depends on the requirements of the individual case. Preferably, in the mixture (1), based in each case on the total amount of the mixture (1),

• 1 to 10, preferably 2 to 8 and in particular 3 to 7% by weight (A),
• - 10 to 80, preferably 15 to 60 and in particular 20 to 50% by weight (B) and
• 19 to 80, preferably 38 to 77 and in particular 47 to 73% by weight (C).

contain.

Suitable are organic and inorganic, especially inorganic, Nanoparticles (A).

The nanoparticles (A) are preferably selected from the group consisting of Compounds of metals of subgroups I to VIII and III. to V. Main groups as well as metals of the I., VII. And VIII. Subgroup of Periodic table of the elements selected. Compounds of Metals of IV., V. and VI. Subgroup and the III. and IV. main group used. In particular, compounds of metals of IV. Subgroup and the III. and IV. Main group used.

The metal compounds (A) are preferably selected from the group consisting of Oxides, oxide hydrates, sulfides, selenides, tellurides, halides, arsenides, Antimonides, nitrides, phosphides, carbides, phosphates, sulfates, carbonates Silicates, titanates, tungstates, zirconates, aluminates and stannates, preferably selected from the group of oxides and hydrated oxides.

• - DE 195 40 623 A1, Spalte 4, Zeile 31, bis Spalte 5, Zeile 30,
• - DE 197 19 948 A1, Seite 2, Zeilen 42 bis 67,
• - DE 197 46 885 A1, Seite 2, Zeilen 42 bis 68, oder
• - WO 00/22052, Seite 5, Zeile 9, bis Seite 6, Zeile 2,

bekannt. Besonders bevorzugt werden Siliziumdioxid, Aluminiumoxid und Aluminiumoxidhydrat eingesetzt. Examples of suitable metals (A) and metal compounds (A) are from the German patent applications

• - DE 195 40 623 A1, column 4, line 31, to column 5, line 30,
• - DE 197 19 948 A1, page 2, lines 42 to 67,
• - DE 197 46 885 A1, page 2, lines 42 to 68, or
• - WO 00/22052, page 5, line 9, to page 6, line 2,

known. Silicon dioxide, aluminum oxide and aluminum oxide hydrate are particularly preferably used.

Hydrophilic fumed silicas are very particularly preferred used, which are not porous, their agglomerates and aggregates one have chain-like structure and which by the flame hydrolysis of Silicon tetrachloride can be produced in a detonating gas flame. These will for example sold by Degussa under the brand Aerosil®. Precipitated water glasses, such as nanohectorites, are also particularly preferred for example from Südchemie under the Optigel® brand or from Laporte are sold under the brand Laponite®.

The further essential component of the mixture (1) is at least one amphiphile (B).

Amphiphiles are known to be molecules that are both hydrophilic and have lipophilic properties (see Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart, New York, 9th edition, 1989, volume 1, page 176, "Amphiphil").

The amphiphiles (B) are preferably selected from the group consisting of Monoalcohols, especially monoalcohols with 3 to 6 carbon atoms in the Molecule, and aliphatic polyols, especially diols with 3 to 12 Carbon atoms in the molecule.

Examples of suitable monoalcohols (B) are propanol, isopropanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, amyl alcohol, neopentyl alcohol or n- Hexanol.

Examples of suitable diols (B) are propylene glycol, trimethylene glycol, Butylene glycol, 1,5-pentanediol, 1,6-hexanediol and the positional isomers Diethyloctanediols, such as those found in German patent application DE 198 09 643 A1 are known.

Propanol, isopropanol, butanol or isobutanol are particularly preferred used.

The further essential constituent of the mixture (1) is at least one, in particular one, compound (C) with at least two, preferably at least three, preferably at least four, particularly preferably at least five and in particular six reactive functional groups that have at least one, contains in particular a bond which can be activated with actinic radiation.

The bonds which can be activated with actinic radiation are preferably formed the group consisting of carbon-hydrogen single bonds or Carbon-carbon, carbon-oxygen, carbon-nitrogen, Carbon-phosphorus or carbon-silicon single bonds or - Double bonds, selected.

Carbon-carbon double bonds ("double bonds") are preferred applied.

The reactive functional groups from which Group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, Vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, Isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, Isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, Norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, selected.

(Meth) acrylate groups are very particularly preferred, in particular Acrylate groups used.

In addition, the compounds (C) can contain at least one, in particular, a reactive functional group that is associated with groups of its kind ("with themselves ") and / or with complementary reactive functional groups Respond. Examples of suitable groups of this type are reactive functional groups (S2) described below, in particular Hydroxyl groups or blocked isocyanate groups.

The basic body to which the double bonds and the optional reactive functional groups is not critical, but can low molecular weight, oligomeric and / or polymeric base bodies are used. The double bonds can be in the usual and known manner optionally polymer-analogous reactions of pendant and / or terminal hydroxyl groups with olefinically unsaturated monoisocyanates, such as Vinyl isocyanate, methacryloyl isocyanate or 1- (1-isocyanato-1-methylethyl) -3- (1- methylethenyl) benzene (TMI® from the company CYTEC), from lateral and / or terminal isocyanate groups with hydroxyl-containing olefinic unsaturated monomers such as hydroxyethyl acrylate or from pendant and / or terminal epoxy groups with olefinically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid.

Examples of suitable constituents (C) which contain up to four double bonds, are used in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Reaktivverdünner", pages 491 and 492, or in the German patent applications DE 198 18 735 A1, column 7, lines 1 to 25, and DE 197 19 948 A1, page 4, lines 19 to 48, or the international Patent application WO 00/22052, page 19, lines 8 to 24.

Examples of suitable components (C) which have six or more double bonds in the Containing molecule are (meth) acrylic functional (meth) acrylic copolymers, Polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, Urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates. Of these, the urethane (meth) acrylates (C) advantageous and are therefore used with particular preference.

The urethane (meth) acrylates (C) and processes for their manufacture are for example from the patent applications and patents EP 0 204 161 A1 DE 196 45 761 A1, WO 98/10028, EP 0 742 239 A1, EP 0 661 321 B1, EP 0 608 021 B1, EP 0 447 998 B1, or EP 0 462 287 B1. The Urethane (meth) acrylates (C) are commercially available products and are for example under the brand Ebecryl® 1290 from UCB, Belgium, or sold under the brand Rahn® 99-664 by the company Rahn.

Further examples of suitable components (C) are from the German Patent application DE 198 18 735 A1, column 2, lines 24 to 36, column 3, line 16 to column 6, line 33, and column 6, lines 34 to 68. Well suited Examples are pentaerythritol triacrylate, which is sold under the trademark Sartomer® 444 D by from Cray Valley, France, and Dipentaerythritol pentaacrylate sold under the Sartomer® 399 brand by the same Company is distributed.

In the process according to the invention, at least one further stage (2) is admixed with the strongly sheared mixture (I) described above with at least one compound (D) of the general formula I:

(S _o L-) _m M (R) _n (H) _p (I),

The compound (D) serves to modify the nanoparticles (A). The Modification by physical adsorption of the compounds (D) on the Surface of the unmodified nanoparticles (A) and / or by chemical Reaction of the compounds (D) with suitable reactive functional groups the surface of the unmodified nanoparticles (A). Preferably the modification takes place via chemical reactions.

In general formula I, the indices and the variables have the following meaning:
S reactive functional group;
L at least double-bonded, linking organic group;
H hydrolyzable, monovalent organic group or hydrolyzable atom;
M bivalent to hexavalent main group and sub group metal;
R non-hydrolyzable, single-membered organic group;
o an integer from 1 to 5, in particular 1;
m + n + p is an integer from 2 to 6, in particular 3 or 4;
p is an integer from 1 to 6, preferably 1 to 4, in particular 3;
m and n are zero or an integer from 1 to 5, preferably 1 to 3, in particular
1, especially m = 1 and n = 0.

Examples of suitable metals M are those described above, in particular Silicon and aluminum.

The reactive functional group S is preferably selected from the group consisting of from (S1) reactive functional groups, at least one with actinic Contain radiation-activatable bond, and (S2) reactive functional Groups with groups of their kind ("with themselves") and / or with complementary reactive functional groups thermally initiated reactions received, selected.

Examples of suitable reactive functional groups (S1) are those above described reactive functional groups with at least one with Binding which can be activated by actinic radiation, in particular methacrylate groups.

Examples of suitable reactive functional groups (S2) are blocked Isocyanate groups, carboxyl groups, anhydride groups, hydroxyl groups, Amino groups and epoxy groups, especially epoxy groups.

The bonds that can be activated with actinic radiation can be Carbon bonds or ether, thioether, carboxylic acid ester, Thiocarboxylic acid ester, carbonate, thiocarbonate, phosphoric acid ester, Thiophosphoric esters, phosphonic esters, thiophosphonic esters, Phosphite, thiophosphite, sulfonic acid ester, amide, amine, thioamide, Phosphoric acid amide, thiophosphoric acid amide, phosphonic acid amide, Thiophosphonic acid amide, sulfonic acid amide, imide, urethane, hydrazide, Urea, thiourea, carbonyl, thiocarbonyl, sulfone or sulfoxide groups, but especially about carbon-carbon bonds, Carboxylic acid ester groups and ether groups, especially carboxylic acid ester groups, be connected to the linking group L.

The variable H stands for a hydrolyzable, single-bonded, organic group or for a hydrolyzable atom.

Examples of suitable hydrolyzable atoms are hydrogen atoms and Halogen atoms, especially chlorine and bromine atoms.

The hydrolyzable, monovalent, organic groups H used.

Examples of suitable groups H of this type are groups of the general formula II:

-XR (II).

In the general formula II, the variable X represents an oxygen atom, a sulfur atom, an oxycarbonyl group and / or a group> NR ¹ , where R ^{1 is} an alkyl group having 1 to 4 carbon atoms, in particular methyl, ethyl, propyl and n-butyl, means. X preferably represents an oxygen atom. The variable R has the meaning given below, methyl and ethyl being particularly preferred here.

R stands for a non-hydrolyzable, single-bonded, organic group. The group R can be substituted or unsubstituted; it is preferably unsubstituted. she can be aromatic, aliphatic or cycloaliphatic. A group R then becomes regarded as aromatic if M and / or X directly with the aromatic Group is connected. This rule is analogous to the aliphatic and Cycloaliphatic groups apply.

Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso- Butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, Ethylene cyclohexane or propane-1,3-diyl-cyclohexane.

Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, Propyl or butyl cyclohex-1-yl.

Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl.

Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl benzene.

Examples of suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.

Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylphen-1-yl.

Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.

The groups R described above can be substituted. For this can be electron-withdrawing or electron-donating atoms or organic Leftovers are used.

Examples of suitable substitutes are halogen atoms, in particular chlorine and Fluorine, nitrile groups, nitro groups, partially or fully halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals, including the examples mentioned above; Aryloxy, alkyloxy and Cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, Propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and Cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, Propylthio, butylthio or cyclohexylthio.

Linear or branched, in particular linear, aliphatic are preferred Leftovers used. Lower aliphatic radicals are preferred. Of these will be the methyl groups or the ethyl groups are used with very particular preference.

The variable L stands for an at least double-binding, in particular double-binding, linking organic group.

• 1. substituierte oder unsubstituierte, bevorzugt unsubstituierte, lineare oder verzweigte, vorzugsweise lineare, Alkandiyl-Reste mit 4 bis 30, bevorzugt 5 bis 20 und insbesondere 6 Kohlenstoffatomen, die innerhalb der Kohlenstoffkette auch cyclische Gruppen enthalten können, insbesondere Trimethylen, Tetramethylen, Pentamethylen, Hexamethylen, Heptamethylen, Octamethylen, Nonan-1,9-diyl, Decan-1,10-diyl, Undecan- 1,11-diyl Dodecan-1,12-diyl, Tridecan-1,13-diyl, Tetradecan-1,14-diyl, Pentadecan-1,15-diyl, Hexadecan-1,16-diyl, Heptadecan-1,17-diyl, Octadecan-1,18-diyl, Nonadecan-1,19-diyl oder Eicosan-1,20-diyl, bevorzugt Tetramethylen, Pentamethylen, Hexamethylen, Heptamethylen, Octamethylen, Nonan-1,9-diyl, Decan-1,10-diyl, 2-Heptyl-1-pentyl- cyclohexan-3,4-bis(non-9-yl), Cyclohexan-1,2-, -1,4- oder -1,3-bis(methyl), Cyclohexan-1,2-, 1,4- oder 1,3-bis(eth-2-yl), Cyclohexan-1,3-bis(prop-3-yl) oder Cyclohexan-1,2-, 1,4- oder 1,3-bis(but-4-yl);
• 2. zweiwertige Polyesterreste mit wiederkehrenden Polyesteranteilen der Formel -(-CO-(CHR⁷)_r-CH₂-O-)- aus. Hierbei ist der Index r bevorzugt 4 bis 6 und der Substitutent R⁷ = Wasserstoff, ein Alkyl-, Cycloalkyl- oder Alkoxy- Rest. Kein Substituent enthält mehr als 12 Kohlenstoffatome;
• 3. lineare Polyetherreste, vorzugsweise mit einem zahlenmittleren Molekulargewicht von 400 bis 5.000, insbesondere von 400 bis 3.000, die sich von Poly(oxyethylen)glykolen, Poly(oxypropylen)glykolen und Poly(oxybutylen)glykolen ableiten;
• 4. lineare Siloxanreste, wie sie beispielsweise in Siliconkautschuken vorliegen, hydrierte Polybutadien- oder Polyisoprenreste, statistische oder alternierende Butadien-Isopren-Copolymerisatreste oder Butadien-Isopren- Pfropfmischpolymerisatreste, die noch Styrol einpolymerisiert enthalten können, sowie Ethylen-Propylen-Dienreste;
• 5. Phen-1,4-, -1,3- oder -1,2-ylen, Naphth-1,4-, -1,3-, -1,2-, -1,5- oder -2,5- ylen, Propan-2,2-di(phen-4'-yl), Methan-di(phen-4'-yl), Diphenyl-4,4'-diyl oder 2,4- oder 2,6-Toluylen; oder
• 6. Cycloalkandiyl-Reste mit 4 bis 20 Kohlenstoffatomen, wie Cyclobutan-1,3- diyl, Cyclopentan-1,3-diyl, Cyclohexan-1,3- oder -1,4-diyl, Cycloheptan-1,4- diyl, Norbornan-1,4-diyl, Adamantan-1,5-diyl, Decalin-diyl, 3,3,5-Trimethyl- cyclohexan-1,5-diyl, 1-Methylcyclohexan-2,6-diyl, Dicyclohexylmethan-4,4'- diyl, 1,1'-Dicyclohexan-4,4'-diyl oder 1,4-Dicyclohexylhexan-4,4"-diyl, insbesondere 3,3,5-Trimethyl-cyclohexan-1,5-diyl oder Dicyclohexylmethan-4,4'-diyl.

Examples of suitable double-bonded organic linking groups L are aliphatic, aromatic, cycloaliphatic and aromatic-cycloaliphatic and heteroatoms containing aliphatic, aromatic, cycloaliphatic and aromatic-cycloaliphatic hydrocarbon radicals, such as

• 1. substituted or unsubstituted, preferably unsubstituted, linear or branched, preferably linear, alkanediyl radicals having 4 to 30, preferably 5 to 20 and in particular 6 carbon atoms, which may also contain cyclic groups within the carbon chain, in particular trimethylene, tetramethylene, pentamethylene, Hexamethylene, heptamethylene, octamethylene, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14 -diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl or eicosane-1,20-diyl , preferably tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonane-1,9-diyl, decane-1,10-diyl, 2-heptyl-1-pentylcyclohexane-3,4-bis (non-9-yl) , Cyclohexan-1,2-, -1,4- or -1,3-bis (methyl), cyclohexan-1,2-, 1,4- or 1,3-bis (eth-2-yl), cyclohexane -1,3-bis (prop-3-yl) or cyclohexane-1,2-, 1,4- or 1,3-bis (but-4-yl);
• 2. divalent polyester residues with recurring polyester components of the formula - (- CO- (CHR ⁷ ) _r -CH ₂ -O -) - from. Here, the index r is preferably 4 to 6 and the substituent R ⁷ = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms;
• 3. linear polyether residues, preferably with a number average molecular weight of 400 to 5,000, in particular 400 to 3,000, which are derived from poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols;
• 4. linear siloxane residues, such as those present in silicone rubbers, hydrogenated polybutadiene or polyisoprene residues, random or alternating butadiene-isoprene copolymer residues or butadiene-isoprene graft copolymer residues, which may also contain copolymerized styrene, and ethylene-propylene-diene residues;
• 5. phen-1,4-, -1,3- or -1,2-ylene, naphth-1,4-, -1,3-, -1,2-, -1,5- or -2, 5- ylene, propan-2,2-di (phen-4'-yl), methane-di (phen-4'-yl), diphenyl-4,4'-diyl or 2,4- or 2,6- toluene; or
• 6. cycloalkanediyl radicals having 4 to 20 carbon atoms, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,3- or -1,4-diyl, cycloheptane-1,4-diyl, Norbornane-1,4-diyl, adamantane-1,5-diyl, decalin-diyl, 3,3,5-trimethylcyclohexane-1,5-diyl, 1-methylcyclohexane-2,6-diyl, dicyclohexylmethane-4, 4'-diyl, 1,1'-dicyclohexane-4,4'-diyl or 1,4-dicyclohexylhexane-4,4 "diyl, in particular 3,3,5-trimethyl-cyclohexane-1,5-diyl or dicyclohexylmethane 4,4'-diyl.

The linking groups L (1) are particularly preferred, very particularly preferably trimethylene, tetramethylene, pentamethylene, hexamethylene, Heptamethylene or octamethylene and especially trimethylene.

The compounds (D) can also be used in a complex form, such as this for example in the international patent application WO 39/52964, page 8, lines 12 to 20.

• - internationalen Patentanmeldung WO 99/52964, Seite 6, Zeile 1, bis Seite 8, Zeile 20,
• - der deutschen Patentanmeldung DE 197 26 829 A1, Spalte 2, Zeile 27, bis Spalte 3, Zeilen 38,
• - der deutschen Patentanmeldung DE 199 10 876 A1, Seite 2, Zeile 35, bis Seite 3, Zeile 12,
• - der deutschen Patentanmeldung DE 38 28 098 A1, Seite 2, Zeile 27, bis Seite 4, Zeile 43,
• - der europäischen Patentanmeldung EP 0 450 625 A1, Seite 2, Zeile 57, bis 5, Zeile 32,
• - der europäischen Patentanmeldung EP 0 872 500 A1, Seite 2, Zeile 32, bis Seite 3, Zeile 12, und Seite 4, Zeile 16, Zeile 53,
• - der deutschen Patentanmeldung DE 197 19 948 A1, Seite 3, Zeile 36, bis Seite 4, Zeile 13, oder
• - der internationalen Patentanmeldung WO 00/22052, Seite 18, Zeile 22, bis Seite 19, Zeile 6,

bekannt. The compounds (D) are customary and known and a large part of them are commercially available. Well suited compounds (D) are for example from the

• - international patent application WO 99/52964, page 6, line 1, to page 8, line 20,
• - German patent application DE 197 26 829 A1, column 2, line 27, to column 3, line 38,
• - German patent application DE 199 10 876 A1, page 2, line 35, to page 3, line 12,
• - German patent application DE 38 28 098 A1, page 2, line 27, to page 4, line 43,
• - European patent application EP 0 450 625 A1, page 2, line 57, to 5, line 32,
• - European patent application EP 0 872 500 A1, page 2, line 32, to page 3, line 12, and page 4, line 16, line 53,
• - German patent application DE 197 19 948 A1, page 3, line 36, to page 4, line 13, or
• - international patent application WO 00/22052, page 18, line 22, to page 19, line 6,

known.

The compounds (D) are preferably selected from the group consisting of 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane, selected. Methacryloyloxypropyltrimethoxysilane is preferably used. These compounds (D) are particularly preferred together with Compounds (D) used, wherein M = aluminum. Examples particularly good Suitable compounds (D) of this type are aluminum tris (ethoxylate), tris (methoxyethylate), tripropylate, triisopropylate, tris (n-butoxide) or tris (sec.- butoxide). The weight ratio of silicon compound (D) can Vary aluminum compound (D) widely; it is preferably included Silicon compound (D): aluminum compound (D) = 20: 1 to 1: 1, preferably 15: 1 up to 1.1: 1 and in particular 10: 1 to 1.2: 1.

The weight ratio of the nanoparticles (A) to the compounds (D) can also vary widely. It depends primarily on the functionality of the Surface of the nanoparticles (A) on the one hand and the functionality of the Compounds (D) on the other hand and the desired degree of modification so that the skilled worker the weight ratio of (A): (D) due to its general If necessary, adjust your specialist knowledge with the help of simple preliminary tests can. The weight ratio of (A): (D) is preferably 1:20 to 0.5: 1, preferably 1:15 to 1: 1 and in particular 1:10 to 2: 1.

Furthermore, water (E) is added in step (2). The water is used for the hydrolysis and condensation of the compounds (D) with the reactive functional groups on the surface of the nanoparticles (A). Preferably the water is added in an amount just sufficient to accomplish the hydrolysis and condensation. The amount of water is added so that local over-concentrations are avoided. This works z. B. by entering the amount of water in the reaction mixture with the help of moisture-laden adsorbents, for. B. silica gel or molecular sieves, water-containing organic solvents, e.g. B. 80% ethanol, or salt hydrates, e.g. B. CaCl ₂ × 6H ₂ O. However, pure water is preferably used.

As hydrolysis and condensation catalysts can proton or compounds and amines which release hydroxyl ions are used. Specific Examples are organic or inorganic acids, such as hydrochloric acid, Sulfuric acid, phosphoric acid, formic acid or acetic acid and organic or inorganic bases such as ammonia, alkali or alkaline earth metal hydroxides, z. As sodium, potassium or calcium hydroxide, and soluble in the reaction medium Amines, e.g. B. lower alkylamines or alkanolamines. Here are volatile acids and bases, especially hydrochloric acid, acetic acid, ammonia or triethylamine prefers.

The resulting mixture is subjected to weak shear in step (2) exposed. The weak shear can be done with the help of common and well known ones Devices such as stirrers of various types, for example anchor stirrers or paddle stirrer.

Step (2) is preferably carried out at a temperature of ° 40 ° C., preferably ≤ 30 ° C. and in particular carried out at room temperature.

The mixture (2) can be sheared for more or less long. Preferably the duration of the shear is 10 minutes to 10 hours, preferably 20 Minutes to 5 hours and especially 30 minutes to 3 hours.

As such, the dispersions according to the invention can be used as coating materials, Adhesives and sealants for the production of coatings, Adhesive layers and seals or for the production of optical moldings and self-supporting foils are used, such as in the patent applications described in the beginning or in German Patent application DE 198 16 136 A1, column 7, line 24, to column 8, line 57, is described.

However, the dispersions according to the invention are preferably used for the preparation of coating materials, adhesives and sealants, especially of Coating materials used.

The content of the coating materials, adhesives and Sealants on the dispersions of the invention can vary widely and depends on the requirements of the individual case. Preferably the Content adjusted so that the coating materials of the invention, Adhesives and sealants, each based on their total amount surface-modified nanoparticles in an amount of 0.05 to 4, preferred 0.07 to 3.5, particularly preferably 0.1 to 3, very particularly preferably 0.15 to 2.5 and in particular 0.2 to 2 wt.% Contain. It is an advantage if the content of the coating materials, adhesives and Sealing compounds on the connections (C), each based on their Total amount, at 5 to 30, preferably 6 to 28, particularly preferably 7 to 26, very particularly preferably 8 to 24 and in particular 10 to 22% by weight. If such a proportion does not have the dispersions of the invention additional amounts of compounds (C) added.

The coating materials, adhesives and sealants according to the invention serve the production of coatings, adhesive layers and seals.

The coatings, adhesive layers and seals according to the invention serve coating, gluing and sealing Motor vehicle bodies and parts thereof, vehicles in the interior and Outside, buildings inside and outside, doors, windows, furniture and hollow glass articles as well as in the context of industrial painting for the Coating, gluing and sealing of plastic parts, small parts, coils, Containers, electrotechnical components and white goods as well as from.

In particular, the coatings serve to increase the scratch and Abrasion resistance and corrosion resistance, improving the Cleaning behavior, improving demolding and reducing the attachment, the creation of an anti-fog effect, the creation of Anti-reflective properties and / or the increase in burst pressure.

Above all, however, the coating materials of the invention are used as clear lacquers for the production of clear coats, in particular in color and / or effect multi-layer paintwork.

For the production of the clearcoats according to the invention Dispersions according to the invention added to customary and known clearcoats. From a methodological point of view, the preparation of the clearcoats of the invention no peculiarities, but takes place with the help of conventional and well-known Mixing methods and devices, such as stirred kettles, Ultraturrax, dissolvers, inline Dissolvers, gear rim dispersers, static mixers, kneaders or extruders.

Suitable clear coats are single or multi-component clear coats, powder clear coats, Powder slurry clearcoats, UV-curable clearcoats or sealers like those from the Patent applications, patent specifications and publications DE 42 04 518 A1, EP 0594068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0604992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A1, US 5,356,669 A1 or US 5,605,965 A1, DE 42 22 194 A1, the product information from BASF Lacke + Farben AG, "Powder Coatings", 1990, the company name of BASF Coatings AG "Powder Coatings, Powder coatings for industrial applications ", January 2000, US 4,268,542 A1, DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE 196 52 813 A1, DE 198 14 471 A1, EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1, EP 0 002 866 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1, DE 20 03 579 B1, WO 97/46549, WO 99/14254, US 5,824,373 A1, US 4,675,234 A1, US 4,634,602 A1, US 4,424,252 A1, US 4,208,313 A1, US 4,163,810 A1, US 4,129,488 A1, US 4,064,161 A1, US 3,974,303 A1, EP 0 844 286 A1, DE 43 03 570 A1, DE 34 07 087 A1, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A1, DE 40 20 316 A1 or DE 41 22 743 A1 are known are.

Solvent-based inputs and solvents are particularly preferred Multi-component clearcoats, such as those in the unpublished German Patent applications DE 100 41 635.7 and DE 101 29 970.2 are described, used.

• 1. mindestens ein Bindemittel mit im statistischen Mittel mindestens einer isocyanatreaktiven funktionellen Gruppe im Molekül.
  • - mindestens ein Vernetzungsmittel, enthaltend im statistischen Mittel mindestens eine blockierte oder unblockierte Isocyanatgruppe und mindestens eine funktionelle Gruppe mit mindestens einer mit aktinischer Strahlung aktivierbaren Bindung im Molekül, wie sie vorstehend beschrieben werden.

These clear coats preferably contain

• 1. at least one binder with a statistical average of at least one isocyanate-reactive functional group in the molecule.
  • - At least one crosslinking agent containing, on average, at least one blocked or unblocked isocyanate group and at least one functional group with at least one bond which can be activated with actinic radiation in the molecule, as described above.

Examples of suitable isocyanate-reactive functional groups are hydroxyl, Thiol and primary and secondary amino groups, in particular Hydroxyl groups.

The binder can also at least one, in particular at least two of the reactive functional groups described above containing at least one bond that can be activated with actinic radiation.

Examples of suitable binders are thermal or thermal and with actinic radiation curable, statistical, alternating and / or block-like constructed linear and / or branched and / or comb-like (Co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (polyadducts)", and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation resins", as well as pages 73 and 74, "Binder".

Examples of suitable (co) polymers (A) are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, Epoxy-amine adducts, polyureas, polyamides, polyimides, polyester Polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, especially polyester.

Of these binders, the (meth) acrylate copolymers and Polyester have particular advantages and are therefore particularly preferred used.

• 1. Monomere, welche mindestens eine Hydroxyl- oder Aminogruppe pro Molekül tragen, wie
  • - Hydroxyalkylester der Acrylsäure, Methacrylsäure oder einer anderen alpha,beta-olefinisch ungesättigten Carbonsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der alpha,beta-olefinisch ungesättigten Carbonsäure mit einem Alkylenoxid wie Ethylenoxid oder Propylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2- Hydroxyethyl-, 2-Hydroxypropyl-, 3-Hydroxypropyl-, 3-Hydroxybutyl-, 4-Hydroxybutylacrylat, -methacrylat, -ethacrylat, -crotonat, -maleinat, -fumarat oder -itaconat; oder Hydroxycycloalkylester wie 1,4- Bis(hydroxymethyl)cyclohexan-, Octahydro-4,7-methano-1H-inden- dimethanol- oder Methylpropandiolmonoacrylat, -monomethacrylat, - monoethacrylat, -monocrotonat, -monomaleinat, -monofumarat oder -monoitaconat; Umsetzungsprodukte aus cyclischen Estern, wie z. B. epsilon-Caprolacton und diesen Hydroxyalkyl- oder -cycloalkylestern;
  • - olefinisch ungesättigte Alkohole wie Allylalkohol;
  • - Polyole wie Trimethylolpropanmono- oder diallylether oder Pentaerythritmono-, -di- oder -triallylether;
  • - Umsetzungsprodukte aus Acrylsäure und/oder Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, oder anstelle des Umsetzungsproduktes eine äquivalenten Menge Acryl- und/oder Methacrylsäure, die dann während oder nach der Polymerisationsreaktion mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, umgesetzt wird;
  • - Aminoethylacrylat, Aminoethylmethacrylat, Allylamin oder N- Methyliminoethylacrylat; und/oder
  • - Acryloxysilan-enthaltende Vinylmonomere, herstellbar durch Umsetzung hydroxyfunktioneller Silane mit Epichlorhydrin und anschließender Umsetzung des Reaktionsproduktes mit (Meth)acrylsäure und/oder Hydroxyalkyl- und/oder -cycloalkylestern der (Meth)Acrylsäure und/oder weiterer hydroxylgruppehaltiger Monomere (a1).
  • - Monomere, welche mindestens eine Säuregruppe pro Molekül tragen, wie
  • - Acrylsäure, beta-Carboxyethylacrylat, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure;
  • - olefinisch ungesättigte Sulfon- oder Phosphonsäuren oder deren Teilester;
  • - Maleinsäuremono(meth)acryloyloxyethylester, Bernsteinsäuremono(meth)acryloyloxyethylester oder Phthalsäuremono(meth)acryloyloxyethylester; oder
  • - Vinylbenzoesäure (alle Isomere), alpha-Methylvinylbenzoesäure (alle Isomere) oder Vinylbenzsolsulfonsäure (alle Isomere).
  • - Monomere, die im wesentlichen oder völlig frei von reaktiven funktionellen Gruppen sind, wie:
    Monomere (a31):
    Im wesentlichen säuregruppenfreie (Meth)acrylsäureester wie (Meth)Acrylsäurealkyl- oder -cycloalkylester mit bis zu 20 Kohlenstoffatomen im Alkylrest, insbesondere Methyl-, Ethyl-, n-Propyl-, n- Butyl-, sec.-Butyl-, tert.-Butyl-, Hexyl-, Ethylhexyl-, Stearyl- und Laurylacrylat oder -methacrylat; cycloaliphatische (Meth)acrylsäureester, insbesondere Cyclohexyl-, Isobornyl-, Dicyclopentadienyl-, Octahydro-4,7- methano-1H-inden-methanol- oder tert.-Butylcyclohexyl(meth)acrylat; (Meth)Acrylsäureoxaalkylester oder -oxacycloalkylester wie Ethoxytriglykol(meth)acrylat und Methoxyoligoglykol(meth)acrylat mit einem Molekulargewicht Mn von vorzugsweise 550 oder andere ethoxylierte und/oder propoxylierte hydroxylgruppenfreie (Meth)Acrylsäurederivate (weitere Beispiele geeigneter Monomere (31) dieser Art sind aus der Offenlegungsschrift DE 196 25 773 A1, Spalte 3, Zeile 65, bis Spalte 4, Zeile 20, bekannt). Diese können in untergeordneten Mengen höherfunktionelle (Meth)Acrylsäurealkyl- oder -cycloalkylester wie Ethylengylkol-, Propylenglykol-, Diethylenglykol-, Dipropylenglykol-, Butylenglykol-, Pentan-1,5-diol-, Hexan-1,6-diol-, Octahydro-4,7-methano- 1H-inden-dimethanol- oder Cyclohexan-1,2-, -1,3- oder -1,4-diol- di(meth)acrylat; Trimethylolpropan-di- oder -tri(meth)acrylat; oder Pentaerythrit-di-, -tri- oder -tetra(meth)acrylat enthalten. Rahmen der vorliegenden Erfindung sind hierbei unter untergeordneten Mengen an höherfunktionellen Monomeren (a31) solche Mengen zu verstehen, welche nicht zur Vernetzung oder Gelierung der Copolymerisate führen, es sei denn, sie sollen in der Form von vernetzten Mikrogelteilchen vorliegen.
    Monomere (a32):
    Vinylester von in alpha-Stellung verzweigten Monocarbonsäuren mit 5 bis 18 C-Atomen im Molekül. Die verzweigten Monocarbonsäuren können erhalten werden durch Umsetzung von Ameisensäure oder Kohlenmonoxid und Wasser mit Olefinen in Anwesenheit eines flüssigen, stark sauren Katalysators; die Olefine können Crack-Produkte von paraffinischen Kohlenwasserstoffen, wie Mineralölfraktionen, sein und können sowohl verzweigte wie geradkettige acyclische und/oder cycloaliphatische Olefine enthalten. Bei der Umsetzung solcher Olefine mit Ameisensäure bzw. mit Kohlenmonoxid und Wasser entsteht ein Gemisch aus Carbonsäuren, bei denen die Carboxylgruppen vorwiegend an einem quaternären Kohlenstoffatom sitzen. Andere olefinische Ausgangsstoffe sind z. B. Propylentrimer, Propylentetramer und Diisobutylen. Die Vinylester können aber auch auf an sich bekannte Weise aus den Säuren hergestellt werden, z. B. indem man die Säure mit Acetylen reagieren läßt. Besonders bevorzugt werden - wegen der guten Verfügbarkeit - Vinylester von gesättigten aliphatischen Monocarbonsäuren mit 9 bis 11 C-Atomen, die am alpha-C-Atom verzweigt sind, eingesetzt. Vinylester dieser Art werden unter der Marke VeoVa® vertrieben (vgl. auch Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, Seite 598).
    Monomere (a33):
    Diarylethylene, insbesondere solche der allgemeinen Formel I:
    
    R²R³C=CR⁴R⁵ (I),
    
    worin die Reste R², R³, R⁴ und R⁵ jeweils unabhängig voneinander für Wasserstoffatome oder substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- oder Arylcycloalkylreste stehen, mit der Maßgabe, dass mindestens zwei der Variablen R², R³, R⁴ und R⁵ für substituierte oder unsubstituierte Aryl-, Arylalkyl- oder Arylcycloalkylreste, insbesondere substituierte oder unsubstituierte Arylreste, stehen. Beispiele geeigneter Alkylreste sind Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, iso-Butyl, tert.-Butyl, Amyl, Hexyl oder 2-Ethylhexyl. Beispiele geeigneter Cycloalkylreste sind Cyclobutyl, Cyclopentyl oder Cyclohexyl. Beispiele geeigneter Alkylcycloalkylreste sind Methylencyclohexan, Ethylencyclohexan oder Propan-1,3-diyl-cyclohexan. Beispiele geeigneter Cycloalkylalkylreste sind 2-, 3- oder 4-Methyl-, -Ethyl-, -Propyl- oder -Butylcyclohex-1-yl. Beispiele geeigneter Arylreste sind Phenyl, Naphthyl oder Biphenylyl, vorzugsweise Phenyl und Naphthyl und insbesondere Phenyl. Beispiele geeigneter Alkylarylreste sind Benzyl oder Ethylen- oder Propan-1,3-diylbenzol. Beispiele geeigneter Cycloalkylarylreste sind 2-, 3- oder 4-Phenylcyclohex-1-yl. Beispiele geeigneter Arylalkylreste sind 2-, 3- oder 4-Methyl-, -Ethyl-, -Propyl- oder - Butylphen-1-yl. Beispiele geeigneter Arylcycloalkylreste sind 2-, 3- oder 4- Cyclohexylphen-1-yl. Vorzugsweise handelt es sich bei den Arylresten R², R³, R⁴ und/oder R⁵ um Phenyl- oder Naphthylreste, insbesondere Phenylreste. Die in den Resten R², R³, R⁴ und/oder R⁵ gegebenenfalls vorhandenen Substituenten sind elektronenziehende oder elektronenschiebende Atome oder organische Reste, insbesondere Halogenatome, Nitril-, Nitro-, partiell oder vollständig halogenierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- und Arylcycloalkylreste; Aryloxy-, Alkyloxy- und Cycloalkyloxyreste; und/oder Arylthio-, Alkylthio- und Cycloalkylthioreste. Besonders vorteilhaft sind Diphenylethylen, Dinaphthalinethylen, cis- oder trans-Stilben oder Vinyliden-bis(4-nitrobenzol), insbesondere Diphenylethylen (DPE), weswegen sie bevorzugt verwendet werden. Im Rahmen der vorliegenden Erfindung werden die Monomeren (b33) eingesetzt, um die Copolymerisation in vorteilhafter Weise derart zu regeln, dass auch eine radikalische Copolymerisation in Batch-Fahrweise möglich ist.
    Monomere (a34):
    Vinylaromatische Kohlenwasserstoffe wie Styrol, Vinyltoluol, Diphenylethylen oder alpha-Alkylstyrole, insbesondere alpha-Methylstyrol.
    Monomere (a35):
    Nitrile wie Acrylnitril und/oder Methacrylnitril.
    Monomere (a36):
    Vinylverbindungen, insbesondere Vinyl- und/oder Vinylidendihalogenide wie Vinylchlorid, Vinylfluorid, Vinylidendichlorid oder Vinylidendifluorid; N- Vinylamide wie Vinyl-N-methylformamid, N-Vinylcaprolactam oder N- Vinylpyrrolidon; 1-Vinylimidazol; Vinylether wie Ethylvinylether, n- Propylvinylether, Isopropylvinylether, n-Butylvinylether, Isobutylvinylether und/oder Vinylcyclohexylether; und/oder Vinylester wie Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpivalat und/oder der Vinylester der 2- Methyl-2-ethylheptansäure.
    Monomere (a37):
    Allylverbindungen, insbesondere Allylether und -ester wie Allylmethyl-, - ethyl-, -propyl- oder -butylether oder Allylacetat, -propionat oder -butyrat.
    Monomere (a38):
    Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 1.000 bis 40.000 und im Mittel 0,5 bis 2,5 ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen; insbesondere Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 2.000 bis 20.000, besonders bevorzugt 2.500 bis 10.000 und insbesondere 3.000 bis 7.000 und im Mittel 0,5 bis 2,5, bevorzugt 0,5 bis 1,5, ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen, wie sie in der DE 38 07 571 A1 auf den Seiten 5 bis 7, der DE 37 06 095 A1 in den Spalten 3 bis 7, der EP 0 358 153 B1 auf den Seiten 3 bis 6, in der US 4,754,014 A1 in den Spalten 5 bis 9, in der DE 44 21 823 A1 oder in der internationalen Patentanmeldung WO 92/22615 auf Seite 12, Zeile 18, bis Seite 18, Zeile 10, beschrieben sind.
    Monomere (a39):
    Olefine wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien.

und/oder

• 1. Epoxidgruppen enthaltende Monomere wie der Glycidylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure oder Allylglycidylether.

Examples of suitable olefinically unsaturated monomers (a) for the preparation of the (meth) acrylate copolymers are

• 1. Monomers which carry at least one hydroxyl or amino group per molecule, such as
  • - Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol esterified with the acid, or by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol- or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofumarate or monoitaconate; Reaction products from cyclic esters, such as. B. epsilon-caprolactone and these hydroxyalkyl or cycloalkyl esters;
  • - olefinically unsaturated alcohols such as allyl alcohol;
  • - Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • - Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or instead of the reaction product, an equivalent amount of acrylic and / or methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;
  • - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate; and or
  • - Acryloxysilane-containing vinyl monomers, which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid and / or other hydroxyl-containing monomers (a1).
  • - Monomers which carry at least one acid group per molecule, such as
  • - Acrylic acid, beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • - Olefinically unsaturated sulfonic or phosphonic acids or their partial esters;
  • - Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester; or
  • - vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers).
  • Monomers which are essentially or completely free of reactive functional groups, such as:
    Monomers (a31):
    Essentially acid group-free (meth) acrylic esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.- Butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethoxytriglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with a molecular weight Mn of preferably 550 or other ethoxylated and / or propoxylated hydroxyl group-free (meth) acrylic acid derivatives (further examples of suitable monomers (31) of this type are from DE 196 25 773 A1, column 3, line 65, to column 4, line 20, is known). These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di-, tri- or tetra (meth) acrylate. In the context of the present invention, minor amounts of higher-functionality monomers (a31) are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, unless they are intended to be in the form of crosslinked microgel particles.
    Monomers (a32):
    Vinyl esters of alpha-branched monocarboxylic acids with 5 to 18 carbon atoms in the molecule. The branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom. Other olefinic starting materials are e.g. B. propylene trimer, propylene tetramer and diisobutylene. The vinyl esters can also be prepared in a manner known per se from the acids, e.g. B. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).
    Monomers (a33):
    Diarylethylenes, in particular those of the general formula I:
    
    R ² R ³ C = CR ⁴ R ⁵ (I),
    
    wherein the radicals R ² , R ³ , R ⁴ and R ⁵ each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ² , R ³ , R ⁴ and R ⁵ stand for substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl. Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diylbenzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl. The aryl radicals R ² , R ³ , R ⁴ and / or R ⁵ are preferably phenyl or naphthyl radicals, in particular phenyl radicals. The substituents optionally present in the radicals R ² , R ³ , R ⁴ and / or R ⁵ are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals. Diphenylethylene, dinaphthaleneethylene, cis- or trans-stilbene or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous, which is why they are preferably used. In the context of the present invention, the monomers (b33) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible.
    Monomers (a34):
    Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.
    Monomers (a35):
    Nitriles such as acrylonitrile and / or methacrylonitrile.
    Monomers (a36):
    Vinyl compounds, especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
    Monomers (a37):
    Allyl compounds, especially allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
    Monomers (a38):
    Polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line 10.
    Monomers (a39):
    Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.

and or

• 1. Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid or allyl glycidyl ether.

Higher functional monomers of the type described above are in generally used in minor amounts. As part of the present Invention are subordinate amounts of higher functional monomers to understand such amounts that are not necessary for crosslinking or gelling the Lead (meth) acrylate copolymers, unless you want to crosslink specifically produce polymeric microparticles.

Depending on the intended use, the (meth) acrylate copolymers have coating material according to the invention a glass transition temperature of -50 ° C. to +110, preferably -30 to +80, preferably -15 to +70, particularly preferably -15 to +50, very particularly preferably -15 to +40 and in particular -15 to + 30 ° C. The acid number is preferably 3 to 100 mg KOH / g. Likewise, their content of isocyanate-reactive groups, in particular Hydroxyl groups, vary widely; their hydroxyl number is preferably from 20 to 300, preferably 30 to 250, particularly preferably 40 to 200, very particularly preferably 60 to 190, in particular 80 to 180 mg KOH / g. Special advantages result from the use of the monomers (a2) 2-hydroxypropyl-, 3- Hydroxypropyl, 3-hydroxybutyl and 4-hydroxybutyl acrylate and methacrylate.

Examples of suitable production processes for (meth) acrylate copolymers (A) are in European patent applications EP 0 767 185 A1, the German Patents DE 22 14 650 B1 or DE 27 49 576 B1 and the American Patents US 4,091,048A1, US 3,781,379 A1, US 5,480,493 A1, US 5,475,073 A1 or US 5,534,598 A1 or in the standard work Houben-Weyl, Methods of organic chemistry, 4th edition, volume 14/1, pages 24 to 255, 1961. The usual reactors for the copolymerization are and known stirred tanks, stirred tank cascades, tubular reactors, Loop reactors or Taylor reactors, such as those in the Patent specifications and patent applications DE 10 71 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, volume 50, number 9, 1995, pages 1409 to 1416 be considered.

Examples of suitable polyesters are in particular aliphatic polyesters on the Base of hexahydrophthalic anhydride. The polyesters are commercially available Products and are sold, for example, under the Desmophen® 2089, A 575 brand and 670 distributed by Bayer AG.

The production of such polyesters is, for example, in the standard work Ullmann's Encyclopedia of Technical Chemistry, 3rd Edition, Volume 14, Urban & Schwarzenberg, Munich, Berlin, 1963, pages 80 to 89 and pages 99 to 105, and in the books: "Résines Alkydes-Polyesters" by J. Bourry, Paris, publisher Dunod, 1952, "Alkyd Resins" by C. R. Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology" by T.C. Patton, Intersience Publishers, 1962.

The introduction of reactive functional groups with at least one through Actinic radiation can be activated by binding polymer-analogous implementation of those described above (Meth) acrylate copolymers with suitable compounds by actinic Contain bonds that can be activated by radiation. For example, you can optionally present side glycidyl groups of (Meth) acrylate copolymers are reacted with (meth) acrylic acid. Or it some of the hydroxyl groups can be reacted with compounds which a free isocyanate group and at least one, especially one, with contain bond that can be activated by actinic radiation. Examples of suitable ones Compounds of this type are 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) - benzene (TMI® from Cytec) or vinyl isocyanate.

The binder content of the clearcoats of the invention can be wide vary and depends primarily on the functionality of the binder on the one hand and the crosslinking agent on the other. The content is preferably based on the solid of a coating material according to the invention 20 to 90, preferably 25 to 85, particularly preferably 30 to 80, very particularly preferably 35 to 75 and in particular 40 to 70% by weight.

The crosslinking agent preferably takes part in both thermal curing as well as in the curing with actinic radiation.

The crosslinking agent contains on average at least one, in particular at least two unblocked or at least two blocked Isocyanate groups in the molecule.

• a) Phenole wie Phenol, Cresol, Xylenol, Nitrophenol, Chlorophenol, Ethylphenol, tert.-Butylphenol, Hydroxybenzoesäure, Ester dieser Säure oder 2,5-di-tert.-Butyl-4-hydroxytoluol;
• b) Lactame, wie ε-Caprolactam, δ-Valerolactam, γ-Butyrolactam oder β- Propiolactam;
• c) aktive methylenische Verbindungen, wie Diethylmalonat, Dimethylmalonat, Acetessigsäureethyl- oder -methylester oder Acetylaceton;
• d) Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, n-Amylalkohol, t-Amylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonopropylether Ethylenglykolmonobutylether, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Propylenglykolmonomethylether, Methoxymethanol, Glykolsäure, Glykolsäureester, Milchsäure, Milchsäureester, Methylolharnstoff, Methylolmelamin, Diacetonalkohol, Ethylenchlorohydrin, Ethylenbromhydrin, 1,3-Dichloro-2-propanol, 1,4-Cyclohexyldimethanol oder Acetocyanhydrin;
• e) Mercaptane wie Butylmercaptan, Hexylmercaptan, t-Butylmercaptan, t- Dodecylmercaptan, 2-Mercaptobenzothiazol, Thiophenol, Methylthiophenol oder Ethylthiophenol;
• f) Säureamide wie Acetoanilid, Acetoanisidinamid, Acrylamid, Methacrylamid, Essigsäureamid, Stearinsäureamid oder Benzamid;
• g) Imide wie Succinimid, Phthalimid oder Maleimid;
• h) Amine wie Diphenylamin, Phenylnaphthylamin, Xylidin, N-Phenylxylidin, Carbazol, Anilin, Naphthylamin, Butylamin, Dibutylamin oder Butylphenylamin;
• i) Imidazole wie Imidazol oder 2-Ethylimidazol;
• j) Harnstoffe wie Harnstoff, Thioharnstoff, Ethylenharnstoff, Ethylenthioharnstoff oder 1,3-Diphenylharnstoff;
• k) Carbamate wie N-Phenylcarbamidsäurephenylester oder 2-Oxazolidon;
• l) Imine wie Ethylenimin;
• m) Oxime wie Acetonoxim, Formaldoxim, Acetaldoxim, Acetoxim, Methylethylketoxim, Diisobutylketoxim, Diacetylmonoxim, Benzophenonoxim oder Chlorohexanonoxime;
• n) Salze der schwefeligen Säure wie Natriumbisulfit oder Kaliumbisulfit;
• o) Hydroxamsäureester wie Benzylmethacrylohydroxamat (BMH) oder Allylmethacrylohydroxamat; oder
• p) substituierte Pyrazole, insbesondere Dimethylpyrazole, oder Triazole; sowie
• q) Gemische dieser Blockierungsmittel, insbesondere Dimethylpyrazol und Triazole, Malonester und Acetessigsäureester oder Dimethylpyrazol und Succinimid.

Examples of suitable blocking agents for isocyanate groups are

• a) phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, tert-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
• b) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;
• c) active methylenic compounds, such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
• d) Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, methylene methylene ether, methyl monomethyl ether, methylene methylene ether, methyl methylene ether, methyl methylene ether, , Glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanhydrin;
• e) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
• f) acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
• g) imides such as succinimide, phthalimide or maleimide;
• h) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
• i) imidazoles such as imidazole or 2-ethylimidazole;
• j) ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
• k) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone;
• l) imines such as ethyleneimine;
• m) oximes such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oxime;
• n) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;
• o) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
• p) substituted pyrazoles, in particular dimethylpyrazoles, or triazoles; such as
• q) Mixtures of these blocking agents, especially dimethylpyrazole and triazoles, malonic esters and acetoacetic acid esters or dimethylpyrazole and succinimide.

In addition, the crosslinking agent contains on average at least one, in particular at least two, functional groups with at least one Actinic radiation activatable bond in the molecule as described above to be discribed.

The crosslinking agent can be made in any manner.

Crosslinking agents which consist of at least one are of particular advantage Polyisocyanate with an isocyanate functionality of at least 2.0 produced become. Preferably the polyisocyanate had an isocyanate functionality of 2.0 to 6.0, preferably 2.0 to 5.0, particularly preferably 2.0 to 4.5 and in particular 2.0 to 3.5. In view of better weather resistance and Resistance to yellowing becomes aliphatic and cycloaliphatic Polyisocyanates are preferably used. Within the scope of the present invention the term "cycloaliphatic diisocyanate" denotes a diisocyanate in which at least one isocyanate group is attached to a cycloaliphatic radical.

Examples of suitable cycloaliphatic polyisocyanates with a Isocyanate functionality of 2.0 is isophorone diisocyanate (= 5-isocyanato-1- isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1- yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3- trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl- cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) - cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2- Diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2- Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate or Dicyclohexylmethane-4,4'-diisocyanate, especially isophorone diisocyanate.

Examples of suitable acyclic aliphatic diisocyanates with a Isocyanate functionality of 2.0 is trimethylene diisocyanate, Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, Ethyl ethylene diisocyanate, trimethyl hexane diisocyanate, heptane methylene diisocyanate or diisocyanates derived from dimer fatty acids as described under the Commercial name DDI 1410 distributed by Henkel and in the Patent specifications WO 97/49745 and WO 97/49747 are described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2- isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane.

Of these, hexamethylene diisocyanate is and will be particularly advantageous therefore very particularly preferably used according to the invention.

Examples of suitable polyisocyanates with an isocyanate functionality> 2 are Polyisocyanates, in particular based on hexamethylene diisocyanate, the Isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, Have carbodiimide and / or uretdione groups and in the usual and known manner available from the diisocyanates described above are. Of these, the allophanate groups are advantageous and are therefore used according to the invention particularly preferably. Example more suitable Manufacturing processes and polyisocyanates are known from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A1, US 4,801,675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 are known.

The polyisocyanates described above are mixed with at least one Compound implemented, the at least one, in particular one, isocyanate-reactive functional group and at least one, especially one, with actinic Contains radiation-activated bond, implemented.

Examples of suitable isocyanate-reactive functional groups are hydroxyl, Thiol and / or primary and / or secondary amino groups, in particular Hydroxyl groups.

Examples of suitable bonds which can be activated with actinic radiation are described above.

• - Allylalkohol oder 4-Butylvinylether;
• - Hydroxyalkylester und Hydroxycycloalkylester der Acrylsäure oder der Methacrylsäure, insbesondere der Acrylsäure, die durch Veresterung aliphatischer Diole, beispielsweise der vorstehend beschriebenen niedermolekularen Diole B), mit Acrylsäure oder Methacrylsäure oder durch Umsetzung von Acrylsäure oder Methacrylsäure mit einem Alkylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Acrylsäure oder Methacrylsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2-Hydroxyethyl-, 2-Hydroxypropyl-, 3- Hydroxypropyl-, 3-Hydroxybutyl-, 4-Hydroxybutyl-, Bis(hydroxymethyl)cyclohexanacrylat oder -methacrylat; von diesen sind 2- Hydroxyethylacrylat und 4-Hydroxybutylacrylat besonders vorteilhaft und werden deshalb erfindungsgemäß besonders bevorzugt verwendet; oder
• - Umsetzungsprodukte aus cyclischen Estern, wie z. B. epsilon-Caprolacton, und diesen Hydroxyalkyl- oder -cycloalkylestern.

Examples of suitable compounds having at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, bond which can be activated with actinic radiation are per molecule

• - Allyl alcohol or 4-butyl vinyl ether;
• - Hydroxyalkyl esters and hydroxycycloalkyl esters of acrylic acid or methacrylic acid, in particular acrylic acid, which can be obtained by esterifying aliphatic diols, for example the low-molecular diols B) described above, with acrylic acid or methacrylic acid or by reacting acrylic acid or methacrylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid or methacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane acrylate or methacrylate; Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly advantageous and are therefore used with particular preference in accordance with the invention; or
• - Reaction products from cyclic esters, such as. B. epsilon-caprolactone, and these hydroxyalkyl or cycloalkyl esters.

The implementation does not offer any special methodological features, but is carried out as for example in European patent application EP 0 928 800 A1, page 4, Lines 41 to 54.

Are the clearcoats according to the invention two-component or multi-component systems, the higher-functionality polyisocyanate described above as Crosslinking agents used.

If the clearcoats according to the invention are one-component systems, the Polyisocyanates with at least one of those described above Blocking agent to the corresponding blocked isocyanate groups containing crosslinking agents implemented.

In a first preferred variant, the Crosslinking agent by the implementation of those described above Compounds with the polyisocyanates in a molar ratio that in statistical means still at least one free isocyanate group in the resulting Adduct remains for reaction with those described above Blocking agents are available.

In a second preferred variant, the Crosslinking agent by the implementation of those described above Blocking agent with the polyisocyanates in a molar ratio that in statistical means still at least one free isocyanate group in the adduct remains for the reaction with the compounds described above is available.

In a third preferred variant, the Crosslinking agent by using the compounds and the blocking agents described above in a one-pot process the polyisocyanates.

Regardless of which variant for the production of crosslinking agents free isocyanate groups are no longer present or more detectable.

The content of the crosslinking agents in the clearcoats of the invention can vary widely and depends primarily on the functionality of the Crosslinking agent (A) on the one hand and the functionality of the binder (B) on the other hand. Preferably contains the invention One-component system, based on its solid, 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60 wt .-%.

In addition, the clear lacquer according to the invention can also be customary and known Contain additives in effective amounts, such as from the German patent application DE 199 24 171 A1, page 8, lines 5 to 46, and Page 8, line 61, to page 9, line 32, are known, in particular Photoinitiators, such as those of the Norrish II type, whose mechanism of action an intramolecular variant of the hydrogen abstraction reactions, as they occur in a variety of ways in photochemical reactions (For example, here on Römpp Chemie Lexikon, 9th expanded and revised Edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, referenced), or cationic Photoinitiators (examples here are on Römpp Lexicon lacquers and printing inks, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446, referenced), in particular benzophenones, benzoins or benzoin ethers or phosphine oxides.

All surfaces that need to be painted come through as substrates the paintwork thereon using heat or heat and actinic radiation are not damaged. Suitable substrates consist for example of metals, plastics, wood, ceramics, stone, textile, Fiber-bonded, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well Connected these materials. The surfaces of these materials can already be pre-painted or pre-coated.

In the case of electrically conductive substrates, primers can be used which are produced in the usual and known manner from electrocoat materials (ETL) become. Both anodic (ATL) and cathodic (KTL) Electrodeposition paints, but especially KTL, into consideration.

With the coating according to the invention, primed or not primed plastics such as B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) as well as their polymer blends or the fiber-reinforced composite materials produced with these plastics be painted.

In the case of non-functionalized and / or non-polar substrate surfaces these can be pretreated in a known manner before coating, such as with a plasma or with flame, subjected to or with a Hydro primer.

The clear lacquers according to the invention and the clearcoats according to the invention in automotive series and Refinishing paint as clear and transparent, highly scratch-resistant, high-gloss flexible, chemical resistant, weather resistant, acid and water-resistant, firmly adhering, stone chip-resistant clear coats in the frame of color and / or effect multi-layer coatings.

The multicoat paint systems of the invention can be of various types be produced according to the invention.

• A) Herstellen einer Basislackschicht durch Applikation eines Wasserbasislacks auf das Substrat,
• B) Trocknen der Basislackschicht,
• C) Herstellen einer Klarlackschicht durch Applikation der erfindungsgemäßen Dispersion auf die Basislackschicht und
• D) gemeinsame Härtung der Basislackschicht und der erfindungsgemäßen Klarlackschicht, wodurch die Basislackierung und die erfindungsgemäße Klarlackierung resultieren (Nass-in-nass-Verfahren).

A first preferred variant of the painting process according to the invention comprises the process steps:

• A) producing a basecoat film by applying a waterborne basecoat to the substrate,
• B) drying the basecoat film,
• C) producing a clear coat by applying the dispersion according to the invention to the basecoat and
• D) joint curing of the basecoat film and the clearcoat film of the invention, resulting in the basecoat and the clearcoat of the invention (wet-on-wet process).

This variant is particularly useful when painting plastics special advantages and is therefore used here with particular preference.

• A) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
• B) Härtung der Füllerlackschicht, wodurch die Füllerlackierung resultiert,
• C) Herstellen einer Basislackschicht durch Applikation eines Wasserbasislacks auf die Füllerlackierung,
• D) Trocknen der Basislackschicht,
• E) Herstellen der erfindungsgemäßen Klarlackschicht durch Applikation der erfindungsgemäßen Dispersion auf die Basislackschicht und
• F) gemeinsame Härtung der Basislackschicht und der erfindungsgemäßen Klarlackschicht, wodurch die Basislackierung und die erfindungsgemäße Klarlackierung resultieren (Nass-in-nass-Verfahren).

A second preferred variant of the painting process according to the invention comprises the process steps:

• A) producing a filler lacquer layer by applying a filler to the substrate,
• B) hardening of the filler lacquer layer, resulting in the filler lacquer,
• C) producing a basecoat film by applying a waterborne basecoat to the filler paint,
• D) drying the basecoat film,
• E) producing the clearcoat layer according to the invention by applying the dispersion according to the invention to the basecoat film and
• F) joint curing of the basecoat layer and the clearcoat layer according to the invention, which results in the basecoat and the clearcoat according to the invention (wet-on-wet process).

• A) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
• B) Trocknung der Füllerlackschicht,
• C) Herstellen einer Basislackschicht durch Applikation eines Wasserbasislacks auf die Füllerlackschicht,
• D) Trocknen der Basislackschicht,
• E) Herstellen der erfindungsgemäßen Klarlackschicht durch Applikation der erfindungsgemäßen Dispersion auf die Basislackschicht und
• F) gemeinsame Härtung der Füllerlackschicht, der Basislackschicht und der erfindungsgemäßen Klarlackschicht, wodurch die Füllerlackierung, die Basislackierung und die erfindungsgemäße Klarlackierung resultieren (erweitertes Nass-in-nass-Verfahren).

A third preferred variant of the painting process according to the invention comprises the process steps:

• A) producing a filler lacquer layer by applying a filler to the substrate,
• B) drying the filler lacquer layer,
• C) producing a basecoat layer by applying a waterborne basecoat to the filler layer,
• D) drying the basecoat film,
• E) producing the clearcoat layer according to the invention by applying the dispersion according to the invention to the basecoat film and
• F) joint curing of the filler lacquer layer, the base lacquer layer and the clear lacquer layer according to the invention, which results in the filler lacquer, the basecoat and the clear lacquer coating according to the invention (extended wet-on-wet method).

• A) Abscheiden einer Elektrotauchackschicht auf dem Substrat,
• B) Trocknen der Elektrotauchlackschicht,
• C) Herstellen einer ersten Basislackschicht durch Applikation eines ersten Basislacks auf der Elektrotauchlackschicht,
• D) gemeinsame Härtung der Elektrotauchlackschicht und der ersten Basislackschicht, wodurch die Elektrotauchlackierung und die erste Basislackierung resultieren (Nass-in-nass-Verfahren,
• E) Herstellen einer zweiten Basislackschicht durch Applikation eines zweiten Basislacks auf die erste Basislackierung,
• F) Trocknen der zweiten Basislackschicht,
• G) Herstellen der erfindungsgemäßen Klarlackschicht durch Applikation der erfindungsgemäßen Dispersion auf die Basislackschicht und
• H) gemeinsame Härtung der zweiten Basislackschicht und der erfindungsgemäßen Klarlackschicht, wodurch die zweite Basislackierung und die erfindungsgemäße Klarlackierung resultieren (Nass-in-nass- Verfahren).

A fourth preferred variant of the painting process according to the invention comprises the process steps:

• A) depositing an electrocoating layer on the substrate,
• B) drying the electrocoat layer,
• C) producing a first basecoat by applying a first basecoat to the electrocoat,
• D) joint curing of the electrocoat layer and the first basecoat layer, which results in the electrocoat and the first basecoat (wet-on-wet process,
• E) producing a second basecoat layer by applying a second basecoat to the first basecoat,
• F) drying the second basecoat,
• G) producing the clearcoat layer according to the invention by applying the dispersion according to the invention to the basecoat film and
• H) joint curing of the second basecoat and the clearcoat of the invention, resulting in the second basecoat and the clearcoat of the invention (wet-on-wet process).

The last three variants offer, in particular, the first coat of Automotive bodies have special advantages and are therefore whole here applied particularly preferably.

It is a very special advantage of the clearcoats of the invention manufactured coatings that they are also on already cured Electro dip painting, filler painting, basecoat or usual and known clearcoats adhere so well that they excellent for car refinishing or scratch-resistant finishing from exposed areas of painted automobile bodies.

The application of the clearcoats according to the invention can be carried out by all the usual methods Application methods, such as B. spraying, knife coating, painting, pouring, dipping, Soak, drip or roll. The thing to be coated can Rest the substrate as such, with the application device or system moving becomes. However, the substrate to be coated, in particular a coil, are moved, the application system being at rest relative to the substrate or in appropriately moved.

Spray application methods, such as, for example, are preferably used Compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally associated with hot spray application such as Hot-air hot spraying. The applications can be used at temperatures of max. 70 to 80 ° C are carried out so that suitable application viscosities are achieved become, without a Change or damage to the waterborne basecoat and its If necessary, use overspray to be reprocessed. So it can Hot spraying must be designed so that the clear coat is very short or short is heated in front of the spray nozzle.

The spray booth used for the application can be used, for example, with a optionally operated temperature-controlled circulation with a suitable absorption medium for the overspray, e.g. B. the invention Clear coat itself, is operated.

In general, the electrocoat, the filler, the Basecoat and the clearcoat of the invention in one Applied wet film thickness that after curing with layers for your Functions necessary and advantageous layer thicknesses result. In case of Electrodeposition coating this layer thickness is 10 to 70, preferably 10 to 60, particularly preferably 15 to 50 and in particular 15 to 45 μm; in case of Filler coating is particularly 10 to 150, preferably 10 to 120 preferably 10 to 100 and in particular 10 to 90 μm; in the case of basecoat it is 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 µm; and in the case of the invention Clear coats are 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 microns. But it can also be done the European patent application EP 0 817 614 A1 known Multi-layer construction from an electro-dip coating, a first Basecoat, a second basecoat and an inventive Clear varnish are applied, where the total layer thickness of the first and second base coat is 15 to 40 microns and the layer thickness of the first Base coat is 20 to 50% of said total layer thickness.

Examples of suitable cathodic electrocoat materials and, if applicable, wet-on-wet Processes involving electrocoat layers are described in the Japanese Patent Application 1975-142501 (Japanese Patent Laid-Open JP 52-065534 A2, Chemical Abstracts Unit No. 87: 137427) or den Patents US 4,375,498 A1, US 4,537,926 A1, US 4,761,212 A1, EP 0 529 335 A1, DE 41 25 459 A1, EP 0 595 186 A1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420 A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1, EP 0 192 113 A2, DE 41 26 476 A1 or WO 98/07794 described.

Likewise, suitable fillers, especially aqueous fillers, are also available as Rockfall protection primers or functional layers are designated, for example from the patents US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89, / 10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827 known.

Suitable basecoats, especially waterborne basecoats, and their use for Production of color and / or effect multi-layer coatings, in particular according to the wet-on-wet method, from patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 5 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431 A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1, EP 0 496 205 A1, EP 0 358 979 A1, EP 469 389 A1, DE 24 46 442 A1, DE 34 09 080 A1, DE 195 47 944 A1, DE 197 41 554.7 A1 or EP 0 817 684, column 5, lines 31 to 45.

The electrocoat, filler, basecoat and clear coat of the invention can be thermally cured, and the Filler lacquer layer, basecoat layer and clear lacquer layer according to the invention can cured thermally or thermally and with actinic radiation (dual cure) become. In particular, the clear lacquer layer according to the invention becomes thermal and hardened with actinic radiation.

Curing can take place after a certain period of rest. It can last from 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min to have. The rest period is used, for example, for the course and for degassing the Coats of paint or to evaporate volatile components such as solvents. The rest period can be increased by using elevated temperatures up to 90 ° C and / or by a reduced air humidity <10 g water / kg air, in particular < 5 g / kg of air, supported and / or shortened, if none Damage or changes to the paint layers occur, for example one early full networking.

The thermal hardening has no special features in terms of method, but rather takes place according to the usual and known methods such as heating in one Fan oven or irradiation with IR lamps. Here, the thermal hardening also take place gradually.

The thermal curing advantageously takes place at a temperature of 50 to 200 ° C, particularly preferably 60 to 190 ° C and in particular 80 to 180 ° C for a time of 1 min to 2 h, particularly preferably 2 min to 1 h and especially 3 min to 45 min.

The curing with actinic radiation is preferably carried out with UV radiation and / or electron beams. A dose of 1,000 to 3,000, preferably 1,100 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm ² is preferably used here. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources. In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the lacquer layers. Even in the case of curing with UV radiation, in order to avoid the formation of ozone, work can be carried out under an inert gas or in an oxygen-depleted atmosphere.

For curing with actinic radiation, the usual and known Radiation sources and optical auxiliary measures applied. Examples of suitable ones Radiation sources are flash lamps from VISIT, high or low mercury low-pressure vapor lamps, which are optionally doped with lead, around a Open beam window up to 405 nm, or electron beam sources. The Installations and conditions of these hardening methods are described in R. Holmes, U.V. and E. B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984. Further examples of suitable methods and devices for curing with actinic radiation are described in German patent application DE 198 18 735 A1, Column 10, lines 31 to 61.

In the case of workpieces of complex shape, such as those used for automobile bodies are provided, the areas not accessible to direct radiation (Shadow areas) such as cavities, folds and other design-related Undercuts connected with spot, small area or all-round emitters with an automatic movement device for the irradiation of Cavities or edges (partially) are cured.

The curing can take place in stages, i. H. through multiple Exposure or exposure to actinic radiation. This can also be the case alternate, d. that is, alternating with UV radiation and Electron radiation is cured.

Thermal curing and curing are combined with actinic radiation applied, these methods can be used simultaneously or alternately become. If the two hardening methods are used alternately, can for example, started with thermal hardening and with hardening actinic radiation. In other cases it can turn out to be prove advantageous to start curing with actinic radiation and to end here.

The multicoat paint systems of the invention are outstanding Property profile based on the mechanics, optics, Corrosion resistance and adhesion is very well balanced. So they point multi-layer coatings according to the invention the high required by the market optical quality and interlayer adhesion and no problems like lack of condensation resistance, cracking (mud cracking) or Flow disorders or surface structures in the inventive Clear coats.

In particular, the multi-layer coatings of the invention have one excellent metallic effect, an excellent D.O.I. (distinctiveness of the reflected image) and excellent surface smoothness. they are weatherproof, resistant to chemicals and bird droppings and highly scratch resistant.

Accordingly, the primed or unprimed according to the invention Substrates coated with at least one coating according to the invention are, with a particularly advantageous application technology Property profile a particularly long service life based on what they economically, aesthetically and technically particularly valuable.

Examples Examples 1 to 3 The preparation of the dispersions 1 to 3 according to the invention

For the preparation of the dispersions 1 to 3 according to the invention 40.9 parts by weight of dipentaerythritol pentaacrylate, 35.2 parts by weight of n-propanol and 4.4 parts by weight of silicon dioxide nanoparticles mixed together. In example 1 became Aerosil® 200, in Example 2 Aerosil® 130 and in Example 3 Aerosil® OX 50 used by Degussa. The resulting mixtures were in the first stage for one hour in a pearl mill (Vollrath VSME) ground. The temperatures did not rise above 30 ° C. Subsequently the grinding media were separated.

Mixtures (1.1) to (3.1) obtained in stage (1) were in the second stage (2) each with 10.3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 6.3 Parts by weight of aluminum tris (sec-butoxide) and 3 parts by weight of water mixed. The resulting mixture of step (2) was over an hour stirred at room temperature with a paddle stirrer.

The dispersions of the invention were for all uses suitable, which in the German patent application DE 198 16 136 A1, column 7, Line 51 until column 8, line 57 are described.

Production Example 1 The production of a binder

In a laboratory reactor with a usable volume of 4 l, which is equipped with a stirrer, a dropping funnel for the monomer feed and a dropping funnel for the Initiator inlet, nitrogen inlet tube, thermometer and reflux condenser 650 parts by weight of a fraction became more aromatic Hydrocarbons with a boiling range of 158 to 172 ° C submitted. The Solvent was heated to 140 ° C, after which at this temperature below Stir a monomer mixture of 652 parts by weight of ethylhexyl acrylate, 383 Parts by weight of hydroxyethyl methacrylate, 143 parts by weight of styrene, 213 Parts by weight of 4-hydroxybutyl acrylate and 49 parts by weight of acrylic acid during four hours and an initiator solution of 113 parts by weight of tert. Butyl perethyl hexanoate and 113 parts by weight of the aromatic solvent were metered in evenly over four and a half hours. With the inlets was started at the same time. After the initiator feed had ended, the Editorial mix kept at 140 ° C for two hours and thereafter cooled. The reaction mixture was mixed with a mixture of 1- Diluted methoxypropylacetate-2, butylglycol acetate and butyl acetate. The the resulting binder solution had a solids content of 65% by weight (1 h / 130 ° C). The acid number was 15 mg KOH / g solid resin.

Examples 4 to 8 The production of dual-cure clearcoats and clearcoats according to the invention therefrom

For the production of the dual-cure clearcoats of Examples 4 according to the invention to 8 was first a base coat of 35.9 parts by weight of Binder solution of preparation example 1, 1.0 part by weight of a substituted Hydroxyphenyltriazine (65% in toluene), 1.0 part by weight of N-methyl-2,2,6,6- tetramethyl-piperidinyl ester (Tinuvin® 123 from Ciba Specialty Chemicals), 0.4 parts by weight of a leveling agent (BYK® 306 from Byk Chemie), 0.5 part by weight of Lucirin® TPO (photoinitiator from BASF Aktiengesellschaft), 1.0 part by weight of Genocure® MBF (photoinitiator from the company Rahn), 2.0 parts by weight of Irgacure® 184 (photoinitiator from Specialty Chemicals, Inc.), 10.8 parts by weight of solvent naphtha and 27.4 parts by weight Butyl diglycol acetate.

The base lacquer was then mixed in each case with the dispersion according to the invention from Example 1 and the isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on: trimers hexamethylene diisocyanate; content of isocyanate groups: 12% by weight). In Examples 5 to 8, dipentaerythritol pentaacrylate was additionally added. Table 1 gives an overview of the material composition of the clearcoats of the invention. Table 1 The material composition of the clearcoats according to the invention from Examples 4 to 8

The clearcoats of Examples 4 to 8 were applied using a box doctor degreased glass plates applied in a wet film thickness of 100 µm. The resulting clearcoat films were left for 5 minutes at room temperature and peeled and dried at 80 ° C for 10 minutes. Then were first with UV radiation at a dose of 1,500 mJ / cm2 and then thermally hardened for 20 minutes at 140 ° C.

The scratch resistance was determined using the steel wool test. For this purpose, the flat side of a locksmith's hammer was covered with a layer of steel wool in accordance with DIN 1041. Then the hammer was carefully placed on the clearcoats at a right angle and passed over the clearcoats in a trace without tilting and without additional physical strength. In each test, 10 double strokes had to be carried out over 15 seconds. The damage pattern was graded as follows: Note damage pattern 1 no scratch 2 small number of scratches 3 moderate number of scratches 4 medium number of scratches 5 large number of scratches 6 a lot of scratches

In addition, the damage pattern was determined after 200 double strokes and the Depth of scratches determined qualitatively.

The test results are summarized in Table 2. Table 2 The results of the steel wool scratch test

Examples 9 and 10 The production of multi-layer coatings according to the invention

For example 9, the clearcoat of example 4 was used.

For example 10, the clearcoat of example 5 was used.

The clear coats were sprayed with butyl acetate to a spray viscosity of 185 in DIN 4- Flow cup set and sieved (mesh size 31 µm).

To produce the multi-layer coatings, test panels made of steel were used Electrocoating with a dry film thickness of 18 to 22 µm coated were coated with a water filler. The resulting Water filler layers were baked at 165 ° C for 20 minutes, so that Filler coatings with a dry film thickness of 35 to 40 µm resulted. The Filler finishes were then covered with a black waterborne basecoat a layer thickness of 12 to 15 microns coated, and the resulting Waterborne basecoats were flashed off at 80 ° C for 10 minutes. The clearcoats of Examples 4 and 5 were then wet-in-wet in one Cloister pneumatically applied with a gravity cup gun. The Clearcoat layers were left for 5 minutes at room temperature and during Flash off at 80 ° C for 10 minutes and dry. Then they became first with UV radiation at a dose of 1,500 mJ / cm2 and then during Thermally hardened at 140 ° C for 20 minutes.

The multilayer coatings of the first series according to the invention were tested as follows:
The gloss and haze of the multi-layer coatings were determined in accordance with DIN 67530.

The micro penetration hardness was determined as universal hardness at 25.6 mN with a Fischersope 100 V measured with Vickers diamond pyramid.

The scratch resistance of the multi-layer paintwork was determined after the sand test. For this purpose, the paint surface was loaded with sand (20 g quartz-silver sand 1.5-2.0 mm). The sand was placed in a beaker (floor cut off flat), which was firmly attached to the test panel. The table with the cup and the sand was shaken by means of a motor drive. The movement of the loose sand caused damage to the paint surface (100 double strokes in 20 s). After exposure to sand, the test area was cleaned of abrasion, carefully wiped under a cold water jet and then dried with compressed air. The gloss was measured according to DIN 67530 before and after damage (measuring direction perpendicular to the scratch direction):
In addition, the scratch resistance was determined according to the Amtec-Kistler test known in the art (cf. T. Klimmasch, T. Engbert, Technologietage, Cologne, DFO, Report Volume 32, pages 59 to 66, 1997).

The scratch resistance was also determined using the steel wool test.

The application properties determined in this way are summarized in Table 3. Table 3 Important application properties of the multi-layer coatings of Examples 9 and 10

The results summarized in Table 3 show that the Multi-coat coatings according to the invention have a high gloss, a low gloss Haze, a very good hardness and a particularly high scratch resistance and a showed good reflow behavior.

Examples 11 of 12 The production of clearcoats and Multi-layer coatings according to the invention therefrom

For the production of the clearcoat of Example 11 according to the invention, the dispersion according to the invention of Example 1 used.

For the production of the clearcoat material of Example 12 according to the invention, the dispersion of Example 2 according to the invention used.

For the production of the clearcoats according to the invention from Examples 11 to 12 the master varnish described in Examples 4 to 8 was used.

Trimeric hexamethylene diisocyanate which was blocked with diethyl malonate and ethyl acetoacetate was used as the crosslinking agent (cf. European patent application EP 0 626 888 A1, component C). Table 4 gives an overview of the material composition. Table 4 the material composition of the clearcoats according to the invention from Examples 4 to 8

The production and testing of important application properties of the multi-layer coating systems according to the invention of Examples 11 of 12 was carried out as described in Examples 9 and 10. Table 5 gives an overview of the test results. Table 5 Important application properties of the multi-layer coatings of Examples 9 and 10

The test results in Table 5 demonstrated the high scratch resistance of the clearcoats or multi-coat coatings according to the invention.

Claims (23)

1. Organic dispersions of surface-modified nanoparticles, can be produced by 1. in a first stage containing a mixture A) nanoparticles of at least one type, B) at least one amphiphile and C) at least one compound with at least two reactive functional groups which contain at least one bond which can be activated with actinic radiation, subjected to strong shear, after which the resulting mixture (1) 2. in at least one further step together with a mixture containing A) at least one compound of the general formula I:

(S _o L-) _m M (R) _n (H) _p (I),

where the indices and the variables have the following meaning:
S reactive functional group;
L at least double-bonded, linking organic group;
H hydrolyzable, monovalent organic group or hydrolyzable atom;
M bivalent to hexavalent main group and sub group metal;
R non-hydrolyzable, single-membered organic group;
an integer from 1 to 5;
m + n + p is an integer from 2 to 6;
p is an integer from 1 to 6
m and n are zero or an integer from 1 to 5; and B) water subject to weak shear. 2. Organic dispersions of surface-modified nanoparticles after Claim 1, characterized in that the strong shear of the first Stage (1) is adjustable by a grinder. 3. Organic dispersions of surface-modified nanoparticles after Claim 1 or 2, characterized in that the low shear the second stage (2) is adjustable by a stirring device. 4. Organic dispersions of surface-modified nanoparticles according to one of claims 1 to 3, characterized in that the reactive functional groups S from the group consisting of 1. reactive functional groups which contain at least one bond which can be activated with actinic radiation, and 2. reactive functional groups which undergo thermally initiated reactions with groups of their kind (“with themselves”) and / or with complementary reactive functional groups, to be selected. 5. Organic dispersions of surface-modified nanoparticles, according to one of claims 1 to 4, characterized in that the with bonds activatable from actinic radiation from the group consisting from carbon-hydrogen single bonds or carbon-carbon Carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds, to be selected. 6. Organic dispersions of surface-modified nanoparticles after Claim 5, characterized in that the double bonds Carbon-carbon double bonds ("double bonds") are. 7. Organic dispersions of surface-modified nanoparticles, according to Claim 6, characterized in that the reactive functional Groups (S1) are (meth) acrylate groups. 8. Organic dispersions of surface-modified nanoparticles after one of claims 4 to 7, characterized in that the reactive functional groups (S2) from the group consisting of blocked Isocyanate groups, carboxyl groups, anhydride groups, hydroxyl groups, Amino groups and epoxy groups can be selected. 9. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 8, characterized in that the hydrolyzable, single-bonded, organic group R from the group, consisting of is selected for methyl, ethyl, propyl and n-butyl. 10. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 9, characterized in that the divalent, linking, organic group L from the group, consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, Heptamethylene or octamethylene, especially trimethylene becomes. 11. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 10, characterized in that m + n + p = 3 or 4. 12. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 11, characterized in that M silicon or is aluminum. 13. Organic dispersions of surface-modified nanoparticles according to one of claims 1 to 12, characterized in that the hydrolyzable monovalent groups H from the group consisting of radicals of the general formula II:

-XR (II),

wherein the variable X stands for an oxygen atom, a sulfur atom, an oxycarbonyl group or a group> NR ¹ with R ¹ = an alkyl group with 1 to 4 carbon atoms, and the hydrolyzable atoms H are selected from the group consisting of hydrogen atoms and halogen atoms , 14. Organic dispersions of surface-modified nanoparticles after Claim 13, characterized in that X represents an oxygen atom. 15. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 14, characterized in that the index o = 1. 16. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 15, characterized in that the Compounds (D) from the group consisting of compounds (D) general formula I, in which the indices have the following meaning: m = 1, n = 0 and p = 3 can be selected. 17. Organic dispersions of surface-modified nanoparticles, after one of claims 1 to 16, characterized in that the Compound (D) is 3-methacryloyloxypropyltrimethoxysilane. 18. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 17, characterized in that the Nanoparticles (A) from the group consisting of compounds of Metals of subgroups I to VIII and III. to V. main group as well from metals of subgroups I, VII and VIII of the periodic system of the elements to be selected. 19. Organic dispersions of surface-modified nanoparticles after Claim 18, characterized in that the metal compounds (A) from the group consisting of oxides, oxide hydrates, sulfides, selenides, Tellurides, halides, arsenides, antimonides, nitrides, phosphides, Carbides, phosphates, sulfates, carbonates, silicates, titanates, Tungstates, zirconates, aluminates and stannates. 20. Organic dispersions of surface-modified nanoparticles after Claim 19, characterized in that the metal compounds (A) Oxides and hydrated oxides are. 21. Organic dispersions of surface-modified nanoparticles after one of claims 1 to 20, characterized in that the Amphiphiles (B) from the group consisting of monoalcohols and aliphatic polyols. 22. A process for the preparation of organic dispersions according to any one of claims 1 to 21, characterized in that 1. in a first stage containing a mixture A) nanoparticles of at least one type, B) at least one amphiphile and C) at least one compound with at least two reactive functional groups which contain at least one bond which can be activated with actinic radiation, subjected to a strong shear gradient at temperatures ≤ 40 ° C, after which the resulting mixture (1) 2. in at least one further step together with a mixture containing A) at least one compound of the general formula I:

(S _o L-) M (R) _n (H) _p (II),

where the indices and the variables have the following meaning:
S reactive functional group;
L at least double-bonded, linking organic group;
H hydrolyzable, monovalent organic group or hydrolyzable atom;
M bivalent to hexavalent main group and sub group metal;
R non-hydrolyzable, single-membered organic group;
an integer from 1 to 5;
m + n + p is an integer from 2 to 6;
p is an integer from 1 to 6
m and n are zero or an integer from 1 to 5; and B) water subject to a weak shear gradient at temperatures ≤ 40 ° C. 23. Use of the organic dispersions of surface-modified Nanoparticles according to one of claims 1 to 21 or according to Claim 22 produced organic dispersions of surface-modified nanoparticles as coating materials, adhesives and sealants or for their manufacture and for their manufacture of molded parts and self-supporting foils.