Oligomers and polymers containing hydrolysates and/or condensates of epoxide groups and silane groups, method for their production and use thereof

Translation of description of equivalent WO 2005049734 A1

Hydrolyzates and / or condensates of epoxy and silane groups containing oligomers and polymers, processes for their preparation and their use

The present invention relates to new hydrolyzates and / or condensates of epoxy and silane groups containing oligomers and polymers. Moreover, the present invention relates to a novel process for the production of hydrolysates and / or condensates of epoxy and silane groups containing oligomers and polymers. Furthermore, the present invention relates to the use of the new hydrolyzates and / or condensates of epoxy and silane groups containing oligomers and polymers as well as the hydrolysates produced by the new process and / or condensates of epoxy and silane groups containing oligomers and polymers as novel curable compositions or to produce new curable compositions. Not least, the present invention relates to the use of the new curable materials for producing new cured compositions, especially coatings and coating systems as well as moldings, especially optical moldings, and self-supporting films.

Curable compositions based on hydrolysates and / or condensates of epoxy-functional silanes are for. B.aus patent applications EP 1179575 A2, WO 00/35599, WO 99/52964, WO 99/54412 A, DE 197 26 829 A 1 or DE 195 40 623 A1. They serve in particular the preparation of highly scratch-resistant coatings.

Curable compositions based on silanes, the at least one olefinically unsaturated group, in particular a vinyl group or

containing methacrylate or acrylate group, such as. for example, vinyltrimethoxysilane or methacryloxypropyltrimethoxysilane (MPTS), are known from Patent applications WO 00/22052, WO 99/54412 A, DE 199 10 876 A1 or DE 197 19 948 A1.

After the international patent application WO 99/54412 A MPTS in the presence of gamma-AlO (OH), for example - hydrolyzed and / or condensed nanoparticles. The resulting gel is evaporated and used as the powder clearcoat. The curing of the applied powder clear coat is carried out thermally.

After the patent applications WO 00/22052 A, DE 199 10 876 A1 or DE 197 19 948 A 1 z. B. are SiO₂Nanoparticles with MPTS silanized and with polyfunctional acrylates, such as, for example, trimethylolpropane triacrylate, mixed. The resulting suspensions can be polymerized with UV radiation or electron radiation.

Thermally curable compositions based on copolymers, the epoxide groups and hydrolyzable Silanlgruppen are included from the American patent US 4,772,672 A is known. The curable compositions must be cured with the help of aluminum or zirconium chelate. The curable compositions can, based on their respective total amount, from 0.1 to 1 wt .-% of water are added to accelerate the cure.

A key objective of these developments is to provide curable compositions for the preparation of cured compositions, especially coatings and coating systems, and of moldings, especially optical moldings, and self-supporting films.

The curable compositions should be simple and well reproducible manner and when used in a liquid state Solids content> 30 wt .-% have, without thereby be affected their transportability, storage stability and processing, in particular their applicability.

The curable compositions are cured compositions, especially coatings and coating systems, especially clearcoats, moldings, especially optical moldings, and provide self-supporting films that are highly scratch resistant and chemically stable. In particular, the coatings and coating systems, especially the clearcoats, even in film thicknesses> 40 .mu.m can be produced without stress cracks occurring is intended. This is an essential prerequisite for the use of coatings and coating systems, especially the clearcoats, in the technologically and esthetically particularly demanding field of automotive OEM (OEM). They must in particular exhibit a particularly high carwash resistance, which makes itself in the relevant practice AMTEC- carwash test by a residual gloss (20 °) to DIN 67530> 70% of the original gloss noticeable.

The previously known curable and cured compositions can, however, this requirement profile does not fully satisfy.

Object of the present invention is to provide new epoxy and silane groups containing substances that allow the preparation of novel curable and cured compositions that meet the above-described requirements in full. In addition, the new epoxy and substances containing silane groups should be simple and well reproducible manner, to present any environmental problems and therefore also require no chemical discharge license. Accordingly, the new hydrolyzates and / or condensates of epoxy and silane groups containing oligomers and polymers have been found which can be produced by reacting oligomer and / or polymer at least one at least one epoxy group (a1) and at least one hydrolyzable silane group (a2) containing (A ) is hydrolyzed and / or condensed.

In the following the new hydrolyzates and / or condensates of epoxy and silane groups (a1) and (a2) containing oligomers and polymers (A) are referred to as "hydrolyzates and / or condensates" according to the invention.

Furthermore, the new process for the preparation of the hydrolysates and / or condensates of the present invention has been found, in which hydrolyzes the oligomers and / or polymers (A) at a pH <7 and / or condenses and the hereinafter referred to as "the invention" becomes.

Not least, the new use of the hydrolysates and / or condensates of the invention and the hydrolyzates and / or condensates produced by the inventive process was found to be curable compositions or for their preparation, which is hereinafter referred to as "inventive use".

Other subjects of the invention will be apparent from the description.

In view of the prior art, it was surprising and for the

Skilled not foreseeable that the object on which the present invention is based, by means of the hydrolysates according to the invention and / or condensates, the method and the use according to the invention could be solved.

It was especially surprising that hydrolysates according to the invention and / or condensates - in particular by the method according to the invention - particularly simple and highly reproducible manufacture were being commercially available starting materials could be used, giving no environmental problems and therefore needed also no chemical discharge license.

In addition, it was surprising that the inventive hydrolysates and / or condensates were outstandingly suitable as new curable compositions or as starting materials for the production of new curable compositions.

The curable compositions were simple and very reproducible manner and could be adjusted to solids contents> 30 wt .-% when using in a liquid state, without affecting their very good transportability, storage stability and processing, in particular their applicability, affected were , Surprisingly, they could also be completely cured quickly without aluminum or zirconium chelate.

The curable compositions of the invention gave new cured compositions, especially coatings and coating systems, especially clearcoats, moldings, especially optical moldings, and self-supporting films that were highly scratch resistant and chemically stable. In particular, let the inventive coatings and coating systems, especially the clearcoats, producing> 40 microns even in film thicknesses, without stress cracks occurring. Therefore the inventive coatings and coating systems, especially the clearcoats, in the technologically and esthetically particularly demanding field of automotive OEM (OEM) could be used. They were characterized mainly by a particularly high carwash resistance and Kratzfestigleit what the basis of the practically oriented AMTEC carwash test by a residual gloss (20 °) to DIN 67530> 70% of the original gloss was underscored.

The hydrolysates and / or condensates of this invention are preparable by reacting epoxy groups and hydrolysable silane groups containing oligomers and / or polymers (A) is preferably hydrolyzed and / or condensed in the framework of the so-called sol-gel method. Its base reactions can be explained by the tetraorthosilicates. These are optionally hydrolyzed in the presence of a co-solvent, and hydrolyzed and / or condensed:

Hydrolysis of Si (OR ')₄ + H₂0 → (R'O)₃Si-OH + ROH

Hydrolysis and / or condensation

-Si-OH + HO-Si- → -Si-O-Si- + H₂O-Si-OH + R'O-Si → Si-O-Si + ROH,

wherein R "is an alkyl group such as methyl or ethyl, may be. To catalyze the reactions acids, bases or fluoride ions are used.

The oligomers (A) contain on average more than 2 and not more than 15 incorporated monomer units. Generally contain Polymers (A) more than 10, preferably more than 15, incorporated monomer units.

The hydrolysates and / or condensates of the present invention can be produced in each case from at least one, especially one, oligomer (A) or polymer (A). For particular applications, but can also mixtures of at least two different oligomers (A), polymer (A) or oligomers and polymers (A) can be used.

The oligomers and polymers (A) contain at least one epoxide group (a1) and at least one in the aforementioned sense hydrolyzable silane (a2). They preferably contain on average at least two, in particular at least three, epoxide groups (a1) and at least two, in particular at least three, hydrolysable silane groups (a2). This may be (a1), be terminal and / or lateral epoxy groups and hydrolysable silane groups (a2).

The oligomers and polymers (A) may have a linear, star or dendrimeric branched or comb-shaped structure. Within an oligomer or polymer (A), these structures can be combined prior to lie. The monomer units may be random, alternating or block distributed, wherein within an oligomer or polymer (A) may be combined with each other these distributions.

The number average and weight average molecular weights and the polydispersity of the molecular weight of the oligomers and polymers (A) may vary widely and depend on the requirements of the case. Preferably, the number average molecular weight is 800 to 3000, preferably 1,000 to 2,500 and in particular 1,000 to 2,000 Dalton. Preferably, the mass average molecular weight is 1000-8000, preferably 1500-6500, and especially 1500-6000 Dalton. Preferably non-uniformity is <10, preferably <8, in particular was <5.

The oligomers and polymers (A) can not be implemented all the polymer classes, in whose preparation and then the epoxide groups (a1) and the hydrolysable silane groups (a2). The skilled worker is therefore easily select the suitable polymer classes due to his general knowledge. Preferably, the oligomers and polymers (A) are addition polymers, especially copolymers of olefinically unsaturated monomers.

The epoxide groups (a1) are connected to the main chain or the main chain of the oligomers and polymers (A) via linking organic groups (G1) covalently linked. It can be linked to the main chain one epoxide (a1) via a divalent linking organic group (G1) or for at least two epoxide groups (a1) an at least trivalent linking organic group (G1). Preferably one epoxide (a1) via a divalent linking organic group (G1) is linked to the main chain.

Preferably group The divalent linking organic groups (G1) at least one, especially one, at least divalent, especially divalent, (G11), selected from the group consisting of substituted and unsubstituted, preferably unsubstituted, branched and unbranched, preferably unbranched, cyclic and non-cyclic, preferably non-cyclic, alkyl, alkenyl and alkynyl groups, especially alkyl groups, and substituted and unsubstituted, preferably unsubstituted, aryl groups, or they consist thereof.

In particular, the double-bonded group (G11) is a straight, non-cyclic, unsubstituted, divalent alkyl of 1 to 10, preferably 2 to 6 and particularly 1 to 4 carbon atoms such as a methylene, ethylene, trimethylene or tetramethylene group.

Preferably the divalent linking organic groups (G1) further comprise at least one, especially one, at least divalent, especially divalent, linking functional group (G12), preferably selected from the group consisting of ether, thioether, carboxylic ester -,

Thiocarboxylate, carbonate, thiocarbonate, phosphate, Thiophosphorsäureester-, phosphonic,

Thiophosphonsäureester-, phosphite, Thiophosphit-, sulfonic acid ester,

Amide, amine, thioamide, Phosphorsäureamid-, Thiophosphorsäureamid-,

Phosphonsäureamid-, Thiophosphonsäureamid-, sulfonamide, imide,

Hydrazide, urethane, urea, thiourea, carbonyl, thiocarbonyl, sulfone or sulfoxide groups, especially carboxylic acid ester groups.

Examples of suitable substituents are halogen atoms, especially fluorine atoms and chlorine atoms, nitrile groups, nitro groups or alkoxy groups. Preferably, the above-described groups (G1) and (G11) are unsubstituted.

Preferably, the epoxide groups (a1) via a group (G11) and this in turn via a group (G12), more preferably according to the general formula I are: - (- G12 -) - (G11 -) - epoxide (I),

connected to the main chain. Specifically, as a group of general formula I

-C (O) -O-CH₂Epoxide (11)

used.

The hydrolysable silane groups (a1) may have different structures. They are preferably selected from the group consisting of hydrolyzable silane groups (a2) of the general formula II: -SiR_mR¹"(II),

selected.

In the general formula II the indices and variables have have the following meanings:

R monovalent, hydrolyzable atom or monovalent hydrolyzable group;

R¹ monovalent non-hydrolysable radical;

m is an integer 1-3, preferably 3, and

n is 0 or 1 or 2, preferably 0 or 1, with the proviso that m + n = 3rd

Examples of suitable monovalent hydrolyzable atoms R are hydrogen, fluorine, chlorine, bromine and iodine.

Examples of suitable monovalent hydrolyzable radicals R are hydroxyl groups, amino groups -NH₂ and groups of the general formula III: R-X- (III),

wherein the variables have the following meanings:

X is oxygen atom, sulfur atom, carbonyl group, thiocarbonyl group, carboxyl group, thiocarboxylic acid-S- ester group, thiocarboxylic acid-O-ester group or amino group - NH- or -NR¹-, Preferably oxygen atom; and

R¹ monovalent organic radical.

The monovalent organic radical R¹ contains at least one group (G2), selected from the group consisting of substituted and unsubstituted, preferably unsubstiuierten, branched and unbranched, preferably unbranched, cyclic and non-cyclic, preferably non-cyclic, alkyl, alkenyl and alkynyl groups, preferably alkyl groups, and substituted and unsubstituted aryl groups; in particular unsubstituted unbranched, non-cyclic alkyl groups; or it consists thereof.

Examples of suitable substituents are those mentioned above. If R is selected from a group (G2), this is monovalent.

Contains R¹ a group (G2), is at least divalent, especially divalent, and linked directly to -X-. Furthermore, the radical R¹ at least one, especially one, of the above-described groups (G12) included.

Contains R¹ at least two groups (G2), at least one of them is at least divalent, especially divalent, and linked directly to -X-. This directly with X- linked group (G2) is associated with at least one other group (G2). Preferably, this directly associated with X- group (G2) (G 12) with the other group (G2) via a group (G12) or the further groups (G2) on at least two groups linked.

Preferably, the radical R¹ from a group (G2). In particular, the radical R is¹ selected from the group consisting of methyl, ethyl, propyl and butyl.

Specifically, the hydrolyzable silane groups (a2) selected from the group consisting of methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl, and tripropoxysilyl tributoxysilyl, especially trimethoxysilyl and triethoxysilyl.

The hydrolysable silane groups (a2) are connected to the main chain or the main chain of the oligomers and polymers (A) preferably over the above-described linking organic groups (G1) covalently linked. Here, a hydrolyzable silane (a2) via a divalent linking organic group (G1) or may be linked to the main chain at least two hydrolysable silane groups (a2) via an at least trivalent linking organic group (G1). Preferably one hydrolyzable silane (a2) via a divalent linking organic group (G1) is linked to the main chain.

Preferably also contain monovalent linking organic groups (G1) at least one, especially one, of the above-described at least divalent, especially divalent, groups (G11) or they consist thereof. Preferably the divalent linking organic groups (G1) further comprise at least one, especially one, of the above-described at least divalent, especially divalent, linking, functional group (G12).

Preferably, the silane groups (a2) via a divalent linking group (G11), which in turn via a divalent linking, functional group (G12) of the general formula (IV) are: - (- G12-HG11 -) - SiR_mR¹_n (IV),

in which the indices and variables are as defined above, linked to the main chain of the oligomers and polymers (A). Very particularly preferred are the following groups of the general formula IV are used:

-C (0) -0 - (- CH₂-) 2-Si (OCH₃)₃ (IV1), -C (0) -0 - (- CH₂-) 3-Si (OCH₃)₃ (IV2) -C (0) -0 - (- CH₂-)₂Si (OC₂H5)₃ (IV3)

-C (0) -0 - (- CH₂-)₃Si (OC₂H₅) 3 (IV4),

-C (0) -0-CH₂Si (OC₂H₅)₃ (IV5)

and

-C (0) -0-CH₂-Themselves₃(OC₂H₅)₂ (IV6)

in particular (IV4).

The molar ratio of epoxide groups (a1) to hydrolysable silane groups (a2) in the oligomers and polymers (A) may vary widely. Preferably it is 1.5: 1 to 1: 1, 5, preferably 1, 3: 1 to 1: 1, 3 and in particular 1.1: 1 to 1: 1.1.

Very especially advantageous are the (meth) acrylate copolymers (A), the lateral and / or terminal epoxide groups (a1) and lateral and / or terminal, hydrolyzable silane groups (a2) of the general formula II:

-SiR_mR¹_n (II)

in which the indices and variables have the meaning indicated above, in a molar ratio of (a1): (a2) = 1, 5: 1 to 1: 1, 5, preferably 1, 3: 1 to 1: 1.3 and especially 1 , 1: 1 to 1: 1.1, included.

This inventive (meth) acrylate copolymers (A) provide especially advantageous hydrolysates according to the invention and / or

Condensates. In addition to the above-described epoxide (a1) and silane groups (a2) may also comprise further lateral and / or terminal groups (a3) ​​the oligomers and polymers (A). It is essential that the groups (a3) ​​do not react with the epoxide groups (a1) and silane groups (a2), or interfere with the course of the hydrolysis and / or condensation. Examples of suitable groups (a3) ​​are fluorine atoms, chlorine atoms, nitrile groups, nitro groups, alkoxy groups,

Polyoxyalkylene or those described above, monovalent organic radicals R¹, In particular aryl groups, alkyl groups and cycloalkyl groups. With the help of this group (a3), the property profile of the oligomers and polymers (A) and thus the hydrolysates and / or condensates of the invention are widely varied advantageously.

The oligomers and polymers (A) containing by copolymerizing at least one, especially one, at least one, especially one, epoxy group (a1) monomer (a1) having at least one, especially one, at least one, especially one, silane group (a2) monomers containing (a2) produced. The monomers (a2) and (a3) ​​can still be at least one monomer (a3) ​​containing at least one group (a3) ​​are copolymerized.

Particular advantages result when the monomers (a1) and (a2) in a molar ratio of (a1): (a2) = 1.5: 1 to 1: 1.5, preferably 1.3: 1 to 1: 1, 3 and especially 1.1: 1 to 1: 1, 1 with each other can be copolymerized. Very particular advantages are obtained if this results in the above-described molar ratio of epoxide groups (a1) to hydrolysable silane groups (a2) in the oligomers and polymers (A). Preferably, the monomers (a1), (a2) and (a3) ​​containing at least one, especially one olefinically unsaturated group.

Examples of suitable olefinically unsaturated groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, Norbomenyl-, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, Norbomenyl-, isoprenyl, isopropenyl, allyl or butenyl ether groups, or dicyclopentadienyl, Norbomenyl-, isoprenyl, isopropenyl, allyl or butenyl, preferably Methcrylatgruppen and acrylate groups, especially methacrylate.

Examples of suitable monomers (a1) are from the American patent US 4,772,672 A, column 5, line 7 to column 6, line 66, known. An example of a particularly suitable monomer (a1) is glycidyl methacrylate.

Examples of suitable monomers (a2) are from the American patent US 4,772,672 A, column 2, line 52, to column 5, line 5 known. An example of an especially suitable monomer (a2) is methacryloxypropyltrimethoxysilane (MPTS), sold under the brand Dynasylan® ® MEMO by Degussa, or methacryloyloxymethyltriethoxysilane or Methacryloxymethyl- methyldiethoxysilane, sold under the trademarks Geniosil® ® XL 34 and XL ® Geniosil® 36 are marketed by the company Wacker.

Examples of suitable monomers (a3) ​​are described in the international patent application WO 03/016411, page 24, line 9 to page 28, line 8,. Preferably, the oligomers and polymers (A) in manner known per se by free-radical copolymerization of the monomers (a1) and (a2) and optionally (a3), preferably in bulk or in solution, in particular in solution, to produce.

The hydrolysates and / or condensates of the present invention are preferably prepared using the method of the invention.

For this purpose, the oligomers and / or polymers described above are (A) is preferably hydrolyzed at a pH <7 and / or condensed. The hydrolysis and / or condensation is carried out in a sol-gel process by reacting with water in the presence of an organic or inorganic acid, preferably an organic acid, in particular acetic acid. Preferably, the hydrolysis and / or condensation at -10 to + 50 is, preferably 0 to + 40, and more particularly carried out + 10 to + 30 ° C.

The hydrolysis and / or condensation, in the presence of customary and known, hydrolyzable, low molecular weight silanes and / or hydrolysable metal alkoxides, as described for example in German patent application DE 199 40 857 A 1, and / or nanoparticles, in particular nanoparticles, performed will.

The nanoparticles are preferably selected from the group consisting of metals, compounds of metals and organic compounds, preferably compounds of metals selected.

Preferably, the metals of the third to fifth main group of three to six and the first and second subgroup of the be Periodic Table of the Elements and the lanthanides, and preferably from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, arsenic, antimony, silver, zinc, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten and cerium selected. In particular, aluminum and silicon are used.

Preferably, in the compounds of the metals to oxides, hydrated oxides, sulfates, hydroxides or phosphates, in particular oxides, hydrated oxides and hydroxides.

Examples of suitable organic compounds are lignins and starches.

The nanoparticles preferably have a primary particle size <50, preferably 5 to 50, especially 5 to 30 nm.

The hydrolysates of the present invention and / or condensates, in particular the hydrolysates produced in the presence of nanoparticles of the invention and / or condensates can be used as such as curable compositions.

Moreover, the hydrolysates according to the invention and / or condensates, in particular the hydrolysates produced in the presence of nanoparticles of the invention and / or condensates, are used to produce curable compositions.

Surprisingly, the nanoparticles described above, in particular when they are cationic stabilized, serve as catalysts for the crosslinking of the hydrolysates according to the invention and / or condensates or the inventive curable compositions, even if these are only subsequently added. As catalysts, the hydrolysates according to the invention and / or condensates or to the curable compositions of the invention can also be compounds of metals with at least one organic, preferably non-aromatic compound to form the chelating ligand can be added as catalysts. The chelate-forming compounds are organic compounds having at least two functional groups that can coordinate to metal atoms or ions. They are usually in these functional groups to electron donors, which donate electrons to metal atoms or ions as electron acceptors. There are in principle all organic compounds of the type stated, as long as they do not adversely affect the crosslinking of the curable compositions of the invention to cured compositions of the invention or even completely prevent. Examples of suitable organic compounds are dimethyl glyoxime, or compounds that contain carbonyl groups in 1,3-position, such as acetylacetone or ethyl acetoacetate. In addition, reference is made to Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart, 1989, Volume 1, page 634th It is also the aluminum and zirconium chelate complexes as described for example in the American patent US 4,772,672 A, column 8, line 1, to column 9, line 49, are used as catalysts. But it is a particular advantage of the curable compositions of the invention that they can be executed without the use of Ghelatkomplexen cured rapidly and completely.

Furthermore, the hydrolysates according to the invention and / or

Condensates or the inventive curable compositions customary, known catalysts for the crosslinking of the epoxide groups, such as Lewis acids, aluminum or tin compounds of amines or heterocycles, are added, as described for example in the book by Bryan Ellis, "Chemistry and Technology of Epoxy Resins", University of Sheffield, Blackie Academic & Professional,.

they can be added In addition, customary and known, typical coatings ingredients. Examples of suitable constituents are described for example in international patent application WO 03/016411, page 14, line 9 to page 35, line 31.

The preparation of the curable compositions of the invention has no special features but instead may be the carried out using in the international patent application WO 03/016411, page 36, lines 13 to 20, described methods and devices.

The curable compositions of the invention comprise conventional organic solvents (see., International patent application WO 03/016411, page 35, lines 12 to 14) and preferably water. This is a particular advantage of the liquid inventive curable compositions that they have a solids content> 30 may have wt .-% ", without thereby be affected their very good transportability, storage stability and processing, in particular their applicability.

The curable compositions of the invention are used to produce the cured compositions of the invention. Preferably, they are employed as pigmented and unpigmented coating materials, especially clearcoat materials, as well as starting materials for moldings, especially optical moldings, and self-supporting film. Preferably, the cured compositions of the invention are pigmented and non-pigmented coatings and coating systems, preferably transparent, in particular clear, clearcoats, moldings, especially optical moldings, and self-supporting films. Very particularly preferred for this purpose the international patent application WO 03/016411, page 41 line 6 to page 43, line 6, the cured compositions clearcoats and clearcoats as part of multicoat color and / or effect paint systems on conventional substrates (cf.. , i. V. m. page 44, line 6 to page 45, line 6).

The preparation of the cured compositions of the invention from the curable compositions of the invention has no special features but instead is with the aid of conventional methods and devices, which are typical for the particular inventive cured composition, performed.

In particular, the curable coating materials with the help of applied are in the international patent application WO 03/016411, page 37, lines 4 to 24, as described, conventional methods and devices on substrates.

The curing of the curable compositions of the invention can, as described in international patent application WO 03/016411, page 38, line 1 to page 41, line 4 will be described, are performed.

The curable compositions of the invention provide new cured

Compositions, especially coatings and coating systems, especially

Clearcoats, moldings, especially optical moldings, and self-supporting films that are highly scratch resistant and chemically stable. be particular to the inventive coatings and coating systems, especially the clearcoats, producing> 40 .mu.m in film thicknesses without stress cracks occurring.

The cured compositions of the invention are therefore outstandingly suitable as a decorative, protective and / or effect, highly scratch-resistant coatings and coating systems on bodies of means of transport of any kind (in particular muscle-powered means of transportation, such as bicycles, carriages or railroad trolleys, aircraft, such as airplanes, helicopters or airships , floating structures, such as ships or buoys, rail vehicles and motor vehicles, such as motorcycles, buses, trucks or automobiles) or parts thereof; of buildings in indoor and outdoor use; of furniture, windows and doors; of plastic molded parts mainly made of polycarbonate, particularly CDs and windows; small industrial parts, coils, containers, and packaging; white goods; films; of optical, electrical and mechanical components, and hollow glassware and articles of everyday use.

In particular, the inventive coatings and coating systems, especially the clearcoats, in the technologically and esthetically particularly demanding field of automotive OEM (OEM) can be used. They are distinguished especially by a particularly high carwash resistance and scratch resistance, which 67530> 70% of the original gloss can be supported on the basis of the practically oriented AMTEC carwash test by a residual gloss (20 °) according to DIN.

Examples example 1

Preparation of a Methacrylate Copolymer (A1)

In a three-necked glass flask equipped with stirrer, reflux condenser, gas inlet and two feed vessels, 669.5 parts by weight Ethoxypropanol were submitted. The initial charge was heated under a nitrogen atmosphere with stirring to 130 ° C. Subsequently, the first feed, consisting of 377 parts by weight Giycidylmethacrylat were 658.5 parts by weight

Methacryloxypropyltrimethoxysilane (Dynasylan ® MEMO) and 48.25 parts by weight of 1,1'-diphenylethylene, and the second feed consisting of 11.75 parts by weight of tert-Butyperoxy 2-ethylhexanoate and 134 parts by weight Ethoxypropanol simultaneously slowly metered starting with stirring for submission , While the first feed stream was metered for two hours, the second feed stream was metered in over 2.5 hours. The resulting reaction mixture was polymerized for five hours at 130 ° C with stirring.

The resulting methacrylate copolymer (A2) was obtained by gel permeation chromatography (solvent: tetrahydrofuran; internal standard: polystyrene) characterized. There were obtained the following values ​​for molecular weight and polydispersity:

Mass-average molecular weight: 3,967 Dalton Number average molecular weight: 1,721 Dalton molecular weight polydispersity: 2.3.

example 2 The preparation of the methacrylate copolymer (A2)

In a three-necked glass flask equipped with stirrer, reflux condenser, gas inlet and two feed vessels, 150 parts by weight Ethoxypropanol were submitted. The initial charge was heated under nitrogen with stirring to 130 ° C. Subsequently, the first feed consisting of 70.36 parts by weight of glycidyl methacrylate, 122.93 parts by weight of methacryloxypropyltrimethoxysilane were 0.7

Parts by weight of 2,5-dihydrofuran, 02 parts by weight of 1,1'-diphenylethylene, and the second feed consisting of 21.02 parts by weight of tert-butyl 2-ethylhexanoate starting slowly metered in simultaneously with stirring for submission. Here, the first inlet during two hours and the second feed stream was metered in over 2.5 hours. The resulting reaction mixture was polymerized for five hours at 130 ° C with stirring.

The resulting methacrylate copolymer (A2) was measured using gel permeation chromatography (solvent: tetrahydrofuran; internal standard: polystyrene) characterized. There were obtained the following values ​​for molecular weight and polydispersity:

Mass-average molecular weight: 3,960 Dalton Number average molecular weight: 1,701 Dalton molecular weight polydispersity: 2.3.

Preparation Example 1

The preparation of cationically stabilized nanoparticles 2.78 parts by weight of boehmite nanoparticles (Disperal.RTM ® P 3 from Sasol Germany) were added with stirring to a mixture of 25 parts by weight of 1N acetic acid and 2.5 parts by weight of deionized water. The resulting mixture was treated for three minutes in an ultrasonic bath until the boehmite nanoparticles had dissolved.

Preparation Example 2

The preparation of cationically stabilized nanoparticles

Preparation Example 1 was repeated, except that 0.1 N acetic acid was used in place of 1N acetic acid.

example 3

The production of clearcoats 3.1 to 3.5 and clearcoats 3.1 to 3.5

General procedure: - solution of nanoparticles according to preparation 1 or 10 wt .-% - in a round glass flask equipped with a magnetic stirrer, the 10 wt .-% strength solution of nanoparticles Preparation Example 2 presented. For this template the methacrylate copolymer (A1) according to Example 1, and deionized water was added. The resulting reaction mixture was stirred for one hour at room temperature. Then isopropanol was added, and the reaction mixture was stirred for four hours at room temperature. The milky reaction mixture clarified and it formed a translucent clearcoat. Table 1 gives an overview of the material composition of the clearcoat materials prepared by this general preparation instructions 3.1 to 3.5. They were easy to transport and storage stable.

Table 1 The physical composition of the clearcoats 3.1 to 3.5

Ingredient Parts by weight in the clear coat: 3.1 3.2 3.3 3.4 3.5

Nanoparticle solution according

Preparation Example 1 10.5 5.25 3.5

Nanoparticle solution according

Preparation Example 2 - - - 6.13 7.0

Solution of Methacrylatco- polymer (A1) according to Example 1 8.75 8.75 8.75 8.75 8.75

Water 5.53 4.42 4.42 3.48 1, 77

Isopropanol 5.53 4.42 4.42 13.99 15.71

The clearcoats 3.1 to 3.5 were pneumatically on with gravity spray-guns

Steel sheets applied, the - had been precoated with an electrocoat, a surfacer coat, and a black waterborne basecoat - in the order listed above another. The Wet film thickness of the applied clearcoat layers 3.1 to 3.5 was chosen so that the cured clearcoats had a dry film thickness of 40 microns. The applied clearcoat layers 3.1 to 3.5 were flashed for 10 minutes at room temperature and thermally cured for 22 minutes at 140 ° C. Thermal curing forced air ovens from Heraeus were used.

It high-gloss, clear clearcoats 3.1 to 3.5 were obtained, which exhibited very good leveling and were free from stress cracks and surface defects such as craters. There the hardness, flexibility and scratch resistance of the clearcoats 3.1 to 3.5 were investigated.

(:; Handle length 800 g: 35 cm weight without shaft) used for carrying out the steel wool scratch test using a hammer to DIN 1041 was. The panels were stored prior to the test for 24 hours at room temperature.

The flat side of the hammer was wrapped with a layer of steel wool and fastened with masking tape at the raised sides. The hammer was placed at right angles onto the clearcoats. The head of the hammer was guided, without tipping and without additional physical force in a track over the surface of the clearcoat.

In each test, 10 double strokes were performed by hand. After each of these individual tests the steel wool was replaced. After exposure, the test were cleaned with a soft cloth from the residues of steel wool. The areas under test were evaluated visually under artificial light and rated as follows:

Rating Damage

1 does not exist

2 low

3 moderate

4 moderate to middling

5 strong

6 very strong

The evaluation was carried out immediately after the end of the experiment.

Table 2 gives an overview of the results. They underscore that the clearcoats 3.1 to 3.5, were hard flexible and highly scratch resistant.

Table 2: The hardness, flexibility and scratch resistance of the clearcoats 3.1 to 3.5

Test clearcoat: 3.1 3.2 3.3 3.4 3.5

Universal hardness at 25.6 mN

[N / mm²] 92 79.2 77.8 77.8 92

relative elastic Low resilience (%) 62.4 60.2 61 7 61 7 62.4

Steel wool scratch test (rating) 1-2 1-2 1-2 1-2 1-2

example 4

The preparation of the clearcoats 4.1 to 4.5 and the clearcoats 4.1 to 4.5

solution of nanoparticles preparation example 1 and water presented - In a round bottom flask equipped with a magnetic stirrer, the 10 wt .-% were. For submission, the methacrylate copolymer (A2) was added as in Example 2 with stirring. The resulting reaction mixture was stirred for one hour at room temperature. Then isopropanol was added thereto, and the resulting reaction mixture was stirred for four hours at room temperature. The milky reaction mixture clarified and it formed a translucent clearcoat.

Table 3 gives an overview of the material composition of the clearcoat materials prepared by this general preparation instructions 4.1 to 4.5. They were easy to transport and storage stable.

Table 3: The material composition of the clearcoats 4.1 to 4.5

Ingredient Parts by weight in clearcoat: 4.1 4.2 4.3 4.4 4.5

Nanoparticle solution according

Preparation Example 1 1 1 1 1 1

Solution of Methacrylatco- polymer (A2) according to

Example 2 3 3.5 4 4.5 5

Water 1, 58 1, 58 1, 58 1, 58 1, 58

Isopropanol 1, 58 1, 58 1, 58 1, 58 1, 58

The clearcoats 4.1 to 4.5 were applied pneumatically with spray-gun on steel panels which - had been precoated with an electrocoat, a surfacer coat, and a black waterborne basecoat - in the order listed above another. The wet film thickness of the applied clearcoat layers 4.1 to 4.5 was chosen so that the cured clearcoats had 4.1 to 4.5 in a dry film thickness of 20 microns. The applied clearcoat layers 4.1 to 4.5 were flashed for 10 minutes at room temperature and thermally cured for 22 minutes at 140 ° C. Thermal curing forced air ovens from Heraeus were used. It high-gloss, clear clearcoats 4.1 to 4.5 were obtained, which exhibited very good leveling and were free from stress cracks and surface defects such as craters. It the scratch resistance after the steel wool scratch test and the chemical stability after BART the clearcoats 4.1 to 4.5 were investigated.

The BART (BASF ACID RESISTANCE TEST) was used to determine the resistance of a Klariackierung to acids, alkalis and water drops. The Klariackierung was exposed to a gradient oven after baking for 30 minutes at 40 ° C of temperature stress. sulphurous acid 6% strength, hydrochloric acid 10% - ig, sodium hydroxide 5% strength, VE (ie, fully demineralized or deionized) water 1.2; Beforehand the test substances (sulfuric acid were 10% and 36% strength 3 or 4 drops) defined applied with a pipette. Following exposure to the substances they were removed under running water and the damage after 24 h in accordance with a predetermined scale assessed visually:

rating appearance

0 no defect

1 slight marking

2 marking / matting / no softening

3 marking / matting / color change / softening

4 cracks / incipient Durchätzuπg

5 clearcoat removed

Each individual mark (spot) was evaluated and the result in the form of a rating for each test substance. Table 4 gives an overview of the results. They underscore that the clearcoats 4.1 to 4.5 were stable and highly scratch resistant to chemicals.

Table 4: The chemical stability and scratch resistance of the clearcoats 4.1 to 4.5

Test clearcoat: 4.1 4.2 4.3 4.4 4.5

Steel wool scratch test (rating) 1-2 1-2 1-2 1-2

BEARD

Sulfuric acid 10% 0 0 0 0 0 sulfuric acid 36% strength 0 0 0 0 0 Hydrochloric acid 10% 1 1 1 1 1 sulfur dioxide 6% strength 0 0 0 0 0 sodium hydroxide solution 5% strength 0 0 0 0 0 DI water 0 0 0 0 0

example 5

The preparation of a condensate of the methacrylate copolymer (A1)

In a round bottom flask made of glass equipped with stirrer, reflux condenser, thermometer, and exterior heating, were 1,502.7 parts by weight of Methacrylate Copolymer (A1) of Example 1, 2693.7 parts by weight of isopropanol, and 365.4 parts by weight of 0.1 N acetic acid introduced and heated with stirring to 70 ° C for three hours. Then 1394.4 parts by weight of solvent naphtha ® were added, after which the resulting reaction mixture was stirred yet another five minutes at 70 ° C. Thereafter, the low-boiling constituents, in particular the water were at 70 ° C by vacuum distillation (3737.9 parts by weight), and there were 2218.3 parts by weight of the condensate obtained. The residual contents of water (0.2 wt .-%) and isopropanol (2.5 wt .-%) were determined by gas chromatography. The condensate was at 40 ° C more than four weeks shelf life. It was outstandingly suitable for producing clearcoats.

example 6

The preparation of Zweikomponentenklariacke 6.1 and 6.2 and the clearcoats 6.1 and 6.2

To prepare the Zweikomponentenklariacks ​​6.1 with 20 parts by weight decanol ® EX-252 (a product of Nagase Chemtex Corporation, Osaka, Japan) and 1 part by weight of a commercial leveling agent (Byk ® 301 from Byk Chemie), 100 parts by weight of the condensate of Example 5, mixed ,

To prepare the Zweikomponentenklariacks ​​6.2 30 parts by weight decanol ® EX-252 were used instead of 20 parts by weight.

The resulting mixtures were respectively 6.1 and 6.2 9.7

Parts by weight of the catalyst from preparation example 1 added. The resulting Zweikomponentenklariacke 6.1 and 6.2 were pneumatically applied by spray-gun on steel panels which - had been precoated with an electrocoat, a surfacer coat, and a black waterborne basecoat - in the order listed above another. The wet film thickness of the applied clearcoat films 6.1 and 6.2 was chosen so that the cured clearcoats 6.1 and 6.2 had a dry film thickness of 40 microns. The applied clearcoat layers 6.1 and 6.2 were flashed for 10 minutes at room temperature while dried for 5 minutes at 60 ° C and for 22 minutes at 140 ° C thermally cured. Thermal curing forced air ovens from Heraeus were used.

The scratch resistance of the clearcoats 6.1 and 6.2 was determined using the carwash test by AMTEC. Their chemical stability was determined using the gradient oven. The results are shown in Table 5. substantiate the high scratch resistance and chemical stability of the clearcoats 6.1 and 6.2.

Table 5: The scratch resistance and chemical stability of the clearcoats 6.1 and 6.2

Test clearcoat: 6.1 6.2

Gradientenofentest:

Start of damage after 24 hours (° C)

Sodium hydroxide 42> 75

Sulfuric acid 46 47 distilled water> 75> 75

Pancreatin 55 60 Tree resin> 75> 75

AMTEC:

Gloss at 20 ° according to DIN 67530 (units):

Initial gloss 83 84

Gloss after injury: without cleaning 54 50 64 76 with cleaning

Residual gloss (%) 77 80