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

p0001The present invention relates to novel hydrolysates and / or condensates of epoxides and silane group-containing oligomers and polymers. The present invention also relates to a novel process for the preparation of hydrolysates and / or condensates of epoxides and silane group-containing oligomers and polymers. Furthermore, the present invention relates to the use of the novel hydrolysates and / or condensates of oligomers and polymers containing epoxide and silane groups, as well as the hydrolysates and / or condensates of epoxides and silane group-containing oligomers and polymers prepared according to the novel process as novel curable compositions For the preparation of new curable compositions. Last but not least, the present invention relates to the use of the novel curable compositions for the production of new cured compositions, in particular of coatings and varnishes, as well as of moldings, in particular of optical moldings, and of cantilevered films.

p0002Curable compositions based on hydrolysates and / or condensates of epoxy-functional silanes are known, for example, from the patent applications <patcit id="pcit0001" dnum="EP1179575A2"><text>EP 1 179 575 A 2</text></patcit>, <patcit id="pcit0002" dnum="WO0035599A"><text>WO 00/35599 A</text></patcit>, <patcit id="pcit0003" dnum="WO9952964A"><text>WO 99/52964 A</text></patcit>, <patcit id="pcit0004" dnum="WO9954412A"><text>WO 99/54412 A</text></patcit>, <patcit id="pcit0005" dnum="DE19726829A1"><text>DE 197 26 829 A 1</text></patcit> or <patcit id="pcit0006" dnum="DE19540623A1"><text>DE 195 40 623 A 1</text></patcit> known. They are used in particular for the production of highly scratch-resistant coatings.

p0003Curable compositions based on silanes which contain at least one olefinically unsaturated group, in particular a vinyl group or a methacrylate or acrylate group, such as, for example, vinyltrimethoxysilane or methacryloxypropyltrimethoxysilane (MPTS), are disclosed in the patent applications <patcit id="pcit0007" dnum="WO0022052A"><text>WO 00/22052 A</text></patcit>, <patcit id="pcit0008" dnum="WO9954412A"><text>WO 99/54412 A</text></patcit>, <patcit id="pcit0009" dnum="DE19910876A1"><text>DE 199 10 876 A 1</text></patcit> or <patcit id="pcit0010" dnum="DE19719948A1"><text>DE 197 19 948 A 1</text></patcit> known.

p0004According to the international patent application <patcit id="pcit0011" dnum="WO9954412A"><text>WO 99/54412 A</text></patcit> MPTS is hydrolyzed and / or condensed in the presence of gamma-AlO (OH) nanoparticles. The resulting gel is evaporated and used as a powder clear lacquer. Curing of the applied powder clear lacquer is effected thermally.

p0005According to the patent applications <patcit id="pcit0012" dnum="WO0022052A"><text>WO 00/22052 A</text></patcit>, <patcit id="pcit0013" dnum="DE19910876A1"><text>DE 199 10 876 A 1</text></patcit> or <patcit id="pcit0014" dnum="DE19719948A1"><text>DE 197 19 948 A 1 </text></patcit>Are, for example, SiO₂Nanoparticles are silanized with MPTS and mixed with polyfunctional acrylates such as, for example, trimethylolpropane triacrylate. The resulting suspensions can be polymerized with UV radiation or electron radiation.

p0006Thermally curable compositions based on copolymers containing epoxide groups and hydrolyzable silane groups are disclosed in the American patent <patcit id="pcit0015" dnum="US4772672A"><text>U.S. 4,772,672</text></patcit> known. The curable masses must be cured with the aid of aluminum or zirconium chelate complexes. 0.1 to 1% by weight of water can be added to the curable compositions, based on their respective total amount, in order to accelerate the curing.

p0007The <patcit id="pcit0016" dnum="DE3716417A1"><text>DE 37 16 417 A1</text></patcit> Curable compositions containing a copolymer comprising as monomeric components an oxirane-containing vinyl monomer and a specific alkoxysilane-containing vinyl monomer, and as crosslinking curing agent at least one aluminum chelate compound and / or a zirconium chelate compound having no hydroxy or alkoxy group combined with the zirconium. The curable compositions are useful as coating compositions.

p0008The <patcit id="pcit0017" dnum="US6620514B1"><text>US 6,620,514 B1</text></patcit> Relates to a process for the preparation of a composition for the manufacture of nanostructured molds and layers comprising contacting an aqueous and / or alcoholic sol of a compound of an element of silicon and the main and secondary metal groups with compounds containing hydrolyzable alkoxy groups and at least one organically modified alkoxysilane or A precondensate derived therefrom, under conditions which lead to (further) hydrolysis of the compounds and subsequent removal of the alcohol formed or already present.

p0009An essential aim of these developments is to provide curable compositions for the production of cured compositions, in particular of coatings and varnishes, as well as of moldings, in particular of optical moldings, and of cantilevered films.

p0010The curable compositions should be readily and reproducibly reproducible and, when used in the liquid state, have a solids content of> 30% by weight, without affecting their transportability, storage stability and processability, in particular their applicability.

p0011The curable compositions are intended to provide cured compositions, in particular coatings and varnishes, especially clear lacquers, moldings, especially optical moldings, and self-supporting films which are highly scratch-resistant and chemically stable. In particular, the coatings and varnishes, especially the clear lacquers, should also be produced in layer thicknesses> 40 μm without stress cracking. This is an essential prerequisite for the use of the coatings and varnishes, in particular the clear lacquering, in the technologically and aesthetically particularly demanding field of automotive OEM finishing. They must above all have a particularly high wash resistance, which is noticeable in the AMTEC wash road test relevant for practice by a residual gloss (20 °) according to DIN 67530> 70% of the initial luster.

p0012However, the curable and hardened masses known hitherto can not fully meet this requirement profile.

p0013It is an object of the present invention to provide novel substances containing epoxide and silane groups which permit the production of new curable and hardened compositions which fully satisfy the above-described requirement profile. In addition, the new substances containing epoxy and silane groups should be easily reproducible in a reproducible manner, do not pose an ecological problem, and therefore do not require any authorization under chemical law.

p0014Accordingly, the hydrolysates and / or condensates of oligomers and polymers (A) containing epoxide and silane groups have been found, the oligomers and polymers (A) being selected from the group of the copolymers of olefinically unsaturated monomers and the hydrolysates and / By hydrolyzing and / or condensing at least one oligomer and / or polymer (A) containing at least one epoxide group (a1) and at least one hydrolyzable silane group (a2) at a pH &lt;7, and wherein the hydrolysates and / or condensates are present in the presence Of at least one kind of cationically stabilized nanoparticles.

p0015The novel hydrolysates and / or condensates of oligomers and polymers (A) containing epoxide and silane groups (a1) and (a2) are referred to as "hydrolysates and / or condensates" according to the invention.

p0016In addition, the novel process for the preparation of the hydrolyzates and / or condensates according to the invention has been found, in which the oligomers and / or polymers (A) are hydrolyzed and / or condensed at a pH &lt;7 and hereinafter referred to as "process according to the invention" becomes.

p0017Finally, the novel use of the hydrolysates and / or condensates according to the invention and the hydrolysates and / or condensates prepared by the process according to the invention have been found as curable compositions or their preparation, which is referred to hereinafter as "use according to the invention".

p0018Other objects of the invention will be apparent from the description.

p0019In view of the state of the art, it was surprising and could not be foreseen for the skilled worker that the task on which the present invention was based could be solved with the aid of the hydrolysates and / or condensates according to the invention, the process according to the invention and the use according to the invention.

p0020In particular, it was surprising that the hydrolyzates and / or condensates according to the invention could be produced particularly simply and very reproducibly by using the process according to the invention, whereby commercially available starting materials could be used, did not present any ecological problems and therefore did not require any authorization under chemical law.

p0021Furthermore, it was surprising that the hydrolysates and / or condensates according to the invention were outstandingly suitable as novel curable compositions or as starting products for the preparation of novel curable compositions.

p0022The curable compositions according to the invention could be prepared simply and very reproducibly and, when used in a liquid state, could be adjusted to solids contents of> 30% by weight, without impairing their very good transportability, storage stability and processability, in particular their applicability . Surprisingly, they could also be rapidly cured completely without aluminum or zirconium chelate complexes.

p0023The curable compositions according to the invention provided new cured compositions, in particular coatings and lacquers, especially clear lacquers, moldings, especially optical moldings, and self-supporting films which were highly scratch-resistant and chemically acceptable. In particular, the coatings and varnishes according to the invention, especially the clear lacquers, can also be produced in layer thicknesses> 40 μm without stress cracking. Therefore, the coatings and varnishes according to the invention, in particular the clear lacquers, could be used in the technologically and aesthetically particularly demanding field of automotive OEM finishing. They were distinguished above all by a particularly high wash resistance and scratch resistance, which could be substantiated by using a residual gloss (20 °) according to DIN 67530> 70% of the initial gloss, based on the practical AMTEC wash road test.

p0024The hydrolysates and / or condensates according to the invention can be prepared by hydrolyzing and / or condensing oligomers and / or polymers (A) containing epoxide groups and hydrolysable silane groups, preferably in the context of the so-called sol-gel process. Its base reactions can be explained using the tetraorthosilicates. These are, if desired, hydrolyzed and / or condensed in the presence of a co-solvent:

hydrolysis

p0025Si (OR ')₄ + H₂O → (R'O)₃Si-OH + R'OH

Hydrolysis and / or condensation

p0026-Si-OH + HO-Si → -Si-O-Si + H₂O         -Si-OH + R'O-Si- → -Si-O-Si- + R'OH, Wherein R 'may be an alkyl group such as methyl or ethyl. Acids, bases or fluoride ions are used for the catalysis of the reactions.

p0027The oligomers (A) contain on average more than 2 and not more than 15 incorporated monomer units. In general, the polymers (A) contain more than 10, preferably more than 15, incorporated monomer units.

p0028The hydrolysates and / or condensates according to the invention can in each case be prepared from at least one, in particular one, oligomer (A) or polymer (A). However, mixtures of at least two different oligomers (A), polymers (A) or oligomers and polymers (A) can also be used for special applications.

p0029The oligomers and polymers (A) each contain at least one epoxide group (a1) and at least one silane group (a2) which can be hydrolyzed in the abovementioned sense. Preferably, they contain, on a statistical average, at least two, in particular at least three, epoxide groups (a1) and at least two, in particular at least three, hydrolyzable silane groups (a2). These may be terminal and / or lateral epoxide groups (a1) and hydrolyzable silane groups (a2).

p0030The oligomers and polymers (A) may have a linear, star-shaped or dendrimer-branched or comb-shaped structure. Within an oligomer or polymer (A), these structures may be combined with one another. The monomer units may be present in a random, alternating or block-like manner, wherein these distributions may be combined with one another within an oligomer or polymer (A).

p0031The numerical and mass-average molecular weights and the nonuniformity of the molecular weight of the oligomers and polymers (A) can vary widely and depend on the requirements of the individual case. The number-average molecular weight is preferably from 800 to 3,000, preferably from 1,000 to 2,500, and in particular from 1,000 to 2,000, daltons. Preferably, the mass-average molecular weight is from 1,000 to 8,000, preferably from 1,500 to 6,500 and especially from 1,500 to 6,000 Dalton. Ununiformity is preferably &lt;10, preferably &lt;8 and in particular &lt;5.

p0032The oligomers and polymers (A) are copolymers of olefinically unsaturated monomers.

p0033The epoxide groups (a1) are covalently linked to the main chain or the main chains of the oligomers and polymers (A) via linking organic groups (G1). An epoxide group (a1) can be linked to the main chain via a divalent linking organic group (G1) or at least two epoxide groups (a1) can be linked to the main chain via an at least three-membered linking organic group (G1). An epoxide group (a1) is preferably linked to the main chain via a dibasic linking organic group (G1).

p0034Preferably, the dibasic, linking organic groups (G1) contain at least one, in particular one, at least two-biped, in particular dibasic, group (G11) selected from the group consisting of substituted and unsubstituted, preferably unsubstituted, branched and unbranched, Cyclic and non-cyclic, preferably non-cyclic, alkyl, alkenyl and alkynyl groups, especially alkyl groups, as well as substituted and unsubstituted, preferably unsubstituted, aryl groups.

p0035In particular, the dibasic group (G11) is a unbranched, non-cyclic, unsubstituted, dibasic alkyl group having 1 to 10, preferably 2 to 6, and in particular 1 to 4 carbon atoms, such as a methylene, ethylene, trimethylene or tetramethylene group.

p0036Preferably, the dibasic, linking organic groups (G1) additionally contain at least one, in particular one, at least two-biped, in particular dibindic, linking, functional group (G12), preferably selected from the group consisting of ether, thioether and carboxylic acid esters Thiophosphite, thiophosphonic acid, phosphite, thiophosphite, sulfonic acid ester, amide, amine, thioamide, phosphoric acid amide, thiophosphoric acid amide, phosphonic acid amide, thiophosphoric acid, phosphoric acid amide, Thiophosphonic acid amide, sulfonamide, imide, hydrazide, urethane, urea, thiourea, carbonyl, thiocarbonyl, sulfone or sulfoxide groups, especially carboxylic ester groups.

p0037Examples of suitable substituents are halogen atoms, in particular fluorine atoms and chloro atoms, nitrile groups, nitro groups or alkoxy groups. Preferably, the above-described groups (G1) and (G11) are unsubstituted.

p0038The epoxy groups (a1) are preferably linked via a group (G11) and this in turn is linked via a group (G12), particularly preferably according to the general formula I:         <b>- (- G12) - (G11 -) - epoxide</b>     <b>(I)</b>, Connected to the main chain. In particular, as a group of the general formula I         <b>-C (O) -O-CH₂epoxide</b>     <b>(I1)</b> Is used.

p0039The hydrolyzable silane groups (a1) can have different structures. They are preferably selected from the group consisting of hydrolyzable silane groups (a2) of the general formula II:         <b>-SiR_mR¹_n</b>     <b>(II)</b>, selected.

p0040In the general formula II, the indices and the variables have the following meaning:<dl id="dl0001"><dt>R</dt><dd>Monovalent, hydrolyzable atom or monovalent, hydrolyzable group;</dd><dt>R¹</dt><dd>Monovalent, non-hydrolysable radical;</dd><dt>m</dt><dd>Integer of 1 to 3, preferably 3, and</dd><dt>n</dt><dd>0 or 1 or 2, preferably 0 or 1,</dd></dl> With the proviso that m + n = 3.

p0041Examples of suitable monovalent, hydrolyzable atoms R are hydrogen, fluorine, chlorine, bromine and iodine.

p0042Examples of suitable monovalent, hydrolyzable radicals R are hydroxyl groups, amino groups -NH₂ And groups of the general formula III:         <b>R¹-X-</b>     <b>(III),</b> Wherein the variables have the following meaning:<dl id="dl0002"><dt>X</dt><dd>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 -NR¹Preferably oxygen; and</dd><dt>R¹</dt><dd>Monobasic, organic radical.</dd></dl>

p0043The monovalent, organic radical R¹ Contains at least one group (G2) selected from the group consisting of substituted and unsubstituted, preferably unsubstituted, branched and unbranched, preferably unbranched, cyclic and noncyclic, preferably noncyclic, alkyl, alkenyl and alkynyl groups, preferably alkyl groups Substituted and unsubstituted aryl groups; In particular unsubstituted, unbranched, non-cyclic alkyl groups; Or it consists of this.

p0044Examples of suitable substituents are the abovementioned.

p0045If the remainder is R¹ From a group (G2), it is unified.

p0046Contains the remainder R¹ A group (G2), this is at least dibasic, in particular dibasic, and is directly linked to -X-. Moreover, the remainder may be R¹ At least one, in particular one, of the groups (G12) described above.

p0047Contains the remainder R¹ At least two groups (G2), at least one of them is at least dibasic, in particular dibasic, and is directly linked to -X-. This group (G2) directly linked to -X- is linked to at least one further group (G2). Preferably, this group (G2) linked directly to -X- is linked to the further group (G2) via a group (G12) or the further groups (G2) via at least two groups (G12).

p0048The radical R is preferably present¹ From a group (G2). In particular, the remainder R¹ From the group consisting of methyl, ethyl, propyl and butyl.

p0049In particular, the hydrolyzable silane groups (a2) are selected from the group consisting of methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl, tripropoxysilyl and tributoxysilyl, especially trimethoxysilyl and triethoxysilyl.

p0050The hydrolyzable silane groups (a2) are covalently linked to the main chain or the main chains of the oligomers and polymers (A) via the above-described linking organic groups (G1). A hydrolyzable silane group (a2) can be linked to the main chain via a dibinding linking organic group (G1) or at least two hydrolyzable silane groups (a2) can be linked to the main chain via an at least three-membered linking organic group (G1). Preferably, a hydrolyzable silane group (a2) is linked to the main chain via a dibasic linking organic group (G1).

p0051Here, too, the monovalent linking organic groups (G1) preferably contain at least one, in particular one, of the above-described at least dibasic, in particular dibasic, groups (G11). Preferably, the dibasic linking organic groups (G1) additionally contain at least one, in particular one, of the at least two-dibasic, in particular dibasic, linking functional group (G12) described above.

p0052Preference is given to the silane groups (a2) via a dinuclear linking group (G11) and this in turn is linked via a dibasic, linking functional group (G12) according to the general formula (IV):         <b>- (- G12 -) - (G11 -) - SiR_mR¹_n</b>     <b>(IV)</b>, Wherein the indices and the variables are as defined above are linked to the backbone of the oligomers and polymers (A). Very particular preference is given to the following groups of the general formula IV:         <b>-C (O) -O - (- CH₂as shown in Fig.₂-Si (OCH₃) "₃</b>     (IV1),         <b>-C (O) -O - (- CH₂as shown in Fig.₃-Si (OCH₃) "₃</b>     (IV2),         <b>-C (O) -O - (- CH₂as shown in Fig.₂-Si (OC₂H₅) "₃</b>     (IV3)         <b>-C (O) -O - (- CH₂as shown in Fig.₃-Si (OC₂H₅) "₃</b>     (IV4),         <b>-C (O) -O-CH₂-Si (OC₂H₅) "₃</b>     (IV5) and         <b>-C (O) -O-CH₂-Themselves₃(OC₂H₅) "₂</b>     (IV6), Especially (IV4).

p0053The molar ratio of epoxide groups (a1) to hydrolyzable silane groups (a2) in the oligomers and polymers (A) can vary widely. It is preferably from 1.5: 1 to 1: 1.5, preferably from 1.3: 1 to 1: 1.3 and in particular from 1.1: 1 to 1: 1.1.

p0054Very particular preference is given to the (meth) acrylate copolymers (A) which have lateral and / or terminal epoxide groups (a1) and lateral and / or terminal, hydrolysable silane groups (a2) of the general formula II:         <b>-SiR_mR¹_n</b>     (II), (A1): (a2) = 1.5: 1 to 1: 1.5, preferably 1.3: 1 to 1: 1.3, and in particular 1, the indices and the variables have the abovementioned meaning , 1: 1 to 1: 1.1. These (meth) acrylate copolymers (A) according to the invention provide very particularly advantageous hydrolysates and / or condensates according to the invention.

p0055In addition to the above-described epoxide groups (a1) and silane groups (a2), the oligomers and polymers (A) may also contain further lateral and / or terminal groups (a3). It is essential that the groups (a3) ​​neither react with the epoxide groups (a1) and silane groups (a2) nor interfere with the sequence of hydrolysis and / or condensation. Examples of suitable groups (a3) ​​are fluorine atoms, chloro atoms, nitrile groups, nitro groups, alkoxy groups, polyoxyalkylene groups or the monovalent organic radicals R described above¹, In particular aryl groups, alkyl groups and cycloalkyl groups. The property profile of the oligomers and polymers (A) and thus of the hydrolysates and / or condensates according to the invention can advantageously be varied broadly with the aid of this group (a3).

p0056The oligomers and polymers (A) are obtainable by copolymerizing at least one, especially one, monomer (a1) containing at least one, in particular one, especially one, at least one, in particular one, silane group (a2), of an epoxide group (a1) (A2) can be produced. The monomers (a2) and (a3) ​​can also be copolymerized with at least one monomer (a3) ​​which contains at least one group (a3).

p0057Particular advantages result when the monomers (a1) and (a2) are present 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 are copolymerized with each other. Very particular advantages are obtained when the above-described molar ratio of epoxide groups (a1) to hydrolyzable silane groups (a2) results in the oligomers and polymers (A).

p0058The monomers (a1), (a2) and (a3) ​​contain at least one, in particular one, olefinically unsaturated group.

p0059Examples of suitable olefinically unsaturated groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, preferably methacrylate groups and acrylate groups, in particular methacrylate groups.

p0060Examples of suitable monomers (a1) are from the American patent <patcit id="pcit0018" dnum="US4772672A"><text>U.S. 4,772,672</text></patcit>, Column 5, line 7, to column 6, line 66. An example of a particularly suitable monomer (a1) is glycidyl methacrylate.

p0061Examples of suitable monomers (a2) are from the American patent <patcit id="pcit0019" dnum="US4772672A"><text>U.S. 4,772,672</text></patcit>, Column 2, line 52, to column 5, line 5. An example of a particularly suitable monomer (a2) is methacryloxypropyltrimethoxysilane (MPTS) marketed under the trademark Dynasilan® MEMO from Degussa, or methacryloxymethyltriethoxysilane or methacryloxymethyl-methyldiethoxysilane sold under the trade names Geniosil® XL 34 and Geniosil® XL 36 by the company Wacker.

p0062Examples of suitable monomers (a3) ​​are described in the international patent application <patcit id="pcit0020" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 24, lines 9 to page 28, line 8.

p0063The oligomers and polymers (A) are preferably preparable in a manner known per se by radical copolymerization of the monomers (a1) and (a2) and optionally (a3), preferably in bulk or in solution, in particular in solution.

p0064The hydrolysates and / or condensates according to the invention are preferably prepared by means of the process according to the invention.

p0065For this purpose, the above-described oligomers and / or polymers (A) are hydrolyzed and / or condensed at a pH of &lt;7. The hydrolysis and / or condensation is carried out in a sol-gel process by reaction with water in the presence of an organic or inorganic acid, preferably an organic acid, in particular acetic acid. The hydrolysis and / or condensation is preferably carried out at -10 to + 50, preferably 0 to + 40 and in particular + 10 to + 30 ° C.

p0066The hydrolysis and / or condensation is carried out in the presence of cationically stabilized nanoparticles and can be carried out in the presence of conventional and known, hydrolyzable, low molecular weight silanes and / or hydrolyzable metal alkoxides as described, for example, in German patent application <patcit id="pcit0021" dnum="DE19940857A1"><text>DE 199 40 857 A 1</text></patcit> , And / or nanoparticles, in particular nanoparticles, can be carried out.

p0067Preferably, the nanoparticles are selected from the group consisting of metals, compounds of metals and organic compounds, preferably compounds of metals.

p0068Preferably, the metals from the third to fifth main group, the third to sixth, and the first and second subgroups of the

p0069And titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, and the like, and the lanthanides, preferably from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, arsenic, antimony And cerium. In particular, aluminum and silicon are used.

p0070Preferably, the compounds of the metals are oxides, oxide hydrates, sulfates, hydroxides or phosphates, in particular oxides, oxide hydrates and hydroxides.

p0071Examples of suitable organic compounds are lignins and starches.

p0072The nanoparticles preferably have a primary particle size &lt;50, preferably 5 to 50, in particular 5 to 30 nm.

p0073The hydrolysates and / or condensates according to the invention, the hydrolysates and / or condensates prepared according to the invention in the presence of nanoparticles, can be used as such as curable compositions.

p0074In addition, the hydrolysates and / or condensates according to the invention, the hydrolysates and / or condensates according to the invention prepared in the presence of nanoparticles, can be used for preparing curable compositions.

p0075Surprisingly, the nanoparticles described above, when they are cationically stabilized, can serve as catalysts for the crosslinking of the inventive hydrolysates and / or condensates or the curable compositions according to the invention.

p0076As catalysts, compounds of metals with at least one organic, preferably non-aromatic, compound capable of forming chelate ligands can also be added as catalysts to the hydrolysates and / or condensates according to the invention or to the curable compositions according to the invention. The chelate ligands forming compounds are organic compounds having at least two functional groups which can coordinate to metal atoms or ions. Usually, these functional groups are electron donors, which emit electrons to metal atoms or ions as electron acceptors. In principle, all organic compounds of the type mentioned are suitable as long as they do not adversely affect or completely prevent the cross-linking of the curable compositions according to the invention to give cured compositions according to the invention. Examples of suitable R organic compounds are dimethyl glyoxime, or compounds that contain carbonyl groups in 1,3-position, such as acetylacetone or ethyl acetoacetate. In addition,<nplcit id="ncit0001" npl-type="b"><text>Römpp Chemistry Lexicon, Georg Thieme Verlag, Stuttgart, 1989, vol. 1, page 634</text></nplcit>, Respectively. It is also possible to use the aluminum and zirconium chelate complexes, as described for example in US Pat<patcit id="pcit0022" dnum="US4772672A"><text>U.S. 4,772,672</text></patcit>, Column 8, line 1, to column 9, line 49, can be used as catalysts. However, it is a particular advantage of the curable compositions according to the invention that they can be rapidly and completely cured without the use of chelate complexes.

p0077Furthermore, conventional and known catalysts for the crosslinking of the epoxide groups, such as Lewis acids, aluminum or tin compounds of amines or heterocycles, can be added to the hydrolysates and / or condensates according to the invention or to the curable compositions according to the invention, as described, for example, in the book by Bryan Ellis , "Chemistry and Technology of Epoxy Resins", University of Sheffield, Blackie Academic &amp; Professional.

p0078In addition, conventional and known, varnish-type constituents can be added to them. Examples of suitable constituents are described, for example, in the international patent application<patcit id="pcit0023" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 14, line 9, to page 35, line 31.

p0079The preparation of the curable compositions according to the invention has no special features, but can be carried out using the methods described in the international patent application <patcit id="pcit0024" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Pages 36, lines 13 to 20, are carried out.

p0080The curable compositions according to the invention contain conventional and known organic solvents (cf. the international patent application <patcit id="pcit0025" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 35, lines 12 to 14) and preferably water. This is a particular advantage of the liquid curable compositions according to the invention that they can have a solids content of> 30% by weight, without thereby affecting their very good transportability, storage stability and processability, in particular their applicability.

p0081The curable compositions according to the invention are used for the preparation of the cured compositions according to the invention. They are preferably used as pigmented and non-pigmented coating materials, in particular clear lacquers, as well as starting products for shaped parts, in particular optical moldings, and free-film.

p0082The cured compositions according to the invention are preferably pigmented and non-pigmented coatings and varnishes, preferably transparent, in particular clear, clear lacquers, moldings, in particular optical moldings, and free-standing films. The cured compositions according to the invention are most particularly preferred for clearcoats and clearcoats in the context of color and / or effect-giving multilayer coatings on customary and known substrates (cf., for this purpose, the international patent application<patcit id="pcit0026" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 41, line 6, to page 43, line 6, i. Page 44, line 6, to page 45, line 6).

p0083The preparation of the hardened compositions according to the invention from the curable compositions according to the invention has no special features, but is carried out with the aid of customary and known processes and devices which are typical for the particular hardened composition according to the invention.

p0084In particular, the curable coating materials according to the invention are produced by means of the methods described in the international patent application <patcit id="pcit0027" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 37, lines 4 to 24, are applied to substrates.

p0085The hardening of the curable compositions according to the invention can be carried out as described in the international patent application <patcit id="pcit0028" dnum="WO03016411A"><text>WO 03/016411</text></patcit>, Page 38, line 1, to page 41, line 4, can be carried out.

p0086The curable compositions according to the invention provide new cured compositions, in particular coatings and varnishes, especially clear lacquers, moldings, especially optical moldings, and cantilever films which are highly scratch-resistant and chemically stable. In particular, the coatings and varnishes according to the invention, especially the clear lacquers, can also be produced in layer thicknesses> 40 μm without stress cracking.

p0087The cured compositions according to the invention are therefore excellently suitable as decorative, protective and / or effectuating, highly scratch-resistant coatings and lacquers of car bodies of any kind of movement (particularly by means of muscle-powered means of transport such as bicycles, carriages or drafts, aircraft such as aircraft, helicopters or zeppelins) , Floating bodies such as ships or buoys, rail vehicles and motor vehicles such as motorcycles, buses, lorries or passenger cars) or parts thereof; Of indoor and outdoor buildings; Of furniture, windows and doors; Of plastic moldings mainly of polycarbonate, in particular CDs and windows; Of industrial parts, of coils, containers and packagings; Of white goods; Of films; Of optical, electro-mechanical and mechanical components, of glassware and articles of daily use.

p0088In particular, the coatings and varnishes according to the invention, in particular the clear lacquers, can be used in the technologically and aesthetically particularly demanding field of automotive OEM finishing. They are distinguished above all by a particularly high wash resistance and scratch resistance, which can be substantiated by the residual-gloss (20 °) according to DIN 67530> 70% of the initial gloss, which is relevant for practice.

Examples

example 1

The preparation of a methacrylate copolymer (A1)

p0089669.5 parts by weight of ethoxypropanol were placed in a three-neck flask of glass, equipped with stirrer, reflux condenser, gas inlet and two feed vessels. The initial charge was heated to 130 ° C. under a nitrogen atmosphere with stirring. Subsequently, the first feed consisting of 377 parts by weight of glycidyl methacrylate, 658.5 parts by weight of methacryloxypropyltrimethoxysilane (Dynasilan® 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 of ethoxypropanol, are added slowly slowly to the initially introduced mixture while stirring. While the first feed was metered in for two hours, the second feed was metered in for 2.5 hours. The resulting reaction mixture was postpolymerized at 130 ° C. for five hours with stirring.

p0090The resulting methacrylate copolymer (A2) was characterized by gel permeation chromatography (solvent: tetrahydrofuran, internal standard: polystyrene). The following values ​​for molecular weight and nonuniformity were obtained:<ul><li>Mass-borne molecular weight: 3,967 daltons</li><li>Molecular weight: 1,721 daltons</li><li>Nonuniformity of the molecular weight: 2.3.</li></ul>

Example 2

The preparation of the methacrylate copolymer (A2)

p0091150 parts by weight of ethoxypropanol were introduced into a three-neck flask of glass, equipped with stirrer, reflux condenser, gas inlet and two feed vessels. The initial charge was heated to 130 ° C under nitrogen and with stirring. Subsequently, the first feed consisting of 70.36 parts by weight of glycidyl methacrylate, 122.93 parts by weight of methacryloxypropyltrimethoxysilane, 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 Tert.-butyl peroxy-2-ethylhexanoate are slowly metered into the receiver simultaneously with stirring, while stirring. The first feed was metered in during two hours and the second feed was metered in for 2.5 hours. The resulting reaction mixture was postpolymerized at 130 ° C. for five hours with stirring.

p0092The resulting methacrylate copolymer (A2) was characterized by means of gel permeation chromatography (solvent: tetrahydrofuran, internal standard: polystyrene). The following values ​​for molecular weight and nonuniformity were obtained:<ul><li>Mass-borne molecular weight: 3,960 daltons</li><li>Molecular weight: 1,701 daltons</li><li>Nonuniformity of the molecular weight: 2.3.</li></ul>

Preparation Example 1

The preparation of cationically stabilized nanoparticles

p00932.78 parts by weight of boehmite nanoparticles (Disperal® 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 in an ultrasonic bath for three minutes until the boehmite nanoparticles had dissolved.

Preparation Example 2

The preparation of cationically stabilized nanoparticles

p0094Preparation Example 1 was repeated except that 0.1 N acetic acid was used instead of the 1N acetic acid.

Example 3

The preparation of clear lacquers 3.1 to 3.5 and clear lacquers 3.1 to 3.5

General preparation:

p0095The 10% strength by weight solution of nanoparticles according to Preparation Example 1 or the 10% strength by weight solution of nanoparticles according to Preparation Example 2 was introduced into a round glass flask equipped with a magnetic stirrer. To this initial charge, the methacrylate copolymer (A1) according to Example 1 and deionized water were added. The resulting reaction mixture was stirred at room temperature for one hour. Then, isopropanol was added and the reaction mixture thus obtained was stirred at room temperature for four hours. The milky cloudy reaction mixture cleared and a translucent clear lacquer formed.

p0096Table 1 gives an overview of the material composition of the clear lacquers 3.1 to 3.5 produced by this general preparation method. They were easy to transport and storage stable.<tables id="tabl0001" num="0001"><table frame="bottom"><title><b>Table 1: The material composition of clear lacquers 3.1 to 3.5</b></title><tgroup cols="6" colsep="0"><colspec colnum="1" colname="col1" colwidth="89mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry morerows="1" rowsep="1" valign="top"><b>component</b></entry><entry namest="col2" nameend="col6" align="left" valign="top"><b>Weight parts in clear lacquer:</b></entry></row><row><entry valign="top"><b>3.1</b></entry><entry valign="top"><b>3.2</b></entry><entry valign="top"><b>3.3</b></entry><entry valign="top"><b>3.4</b></entry><entry valign="top"><b>3.5</b></entry></row></thead><tbody><row><entry valign="bottom">Nanoparticle solution according to Preparation Example 1</entry><entry valign="bottom">10.5</entry><entry valign="bottom">5.25</entry><entry valign="bottom">3.5</entry><entry valign="bottom">-</entry><entry valign="bottom">-</entry></row><row><entry valign="bottom">Nanoparticle solution according to Preparation Example 2</entry><entry valign="bottom">-</entry><entry valign="bottom">-</entry><entry valign="bottom">-</entry><entry valign="bottom">6.13</entry><entry valign="bottom">7.0</entry></row><row><entry valign="bottom">Solution of the methacrylate copolymer (A1) according to Example 1</entry><entry valign="bottom">8.75</entry><entry valign="bottom">8.75</entry><entry valign="bottom">8.75</entry><entry valign="bottom">8.75</entry><entry valign="bottom">8.75</entry></row><row><entry valign="bottom">water</entry><entry valign="bottom">5.53</entry><entry valign="bottom">4.42</entry><entry valign="bottom">4.42</entry><entry valign="bottom">3.48</entry><entry valign="bottom">1.77</entry></row><row><entry valign="bottom">isopropanol</entry><entry valign="bottom">5.53</entry><entry valign="bottom">4.42</entry><entry valign="bottom">4.42</entry><entry valign="bottom">13.99</entry><entry valign="bottom">15.71</entry></row></tbody></tgroup></table></tables>

p0097The clear lacquers 3.1 to 3.5 were applied pneumatically by means of flow-gun guns to steel sheets, which were pre-lacquered in the order listed above with electrocoat coating, a filler lacquer and a black water base lacquer. The wet layer thickness of the applied clearcoat layers 3.1 to 3.5 was selected in such a way that the cured clearcoats had a dry layer thickness of 40 μm. The applied clearcoat layers 3.1 to 3.5 were ventilated for 10 minutes at room temperature and thermally cured at 140 ° C. for 22 minutes. Heraeus recirculating furnaces were used for thermal curing.

p0098High-gloss, clear clear lacquers 3.1 to 3.5 were obtained, which had a very good flow and were free of stress cracks and surface defects such as craters. The hardness, the flexibility and the scratch resistance of the clear lacquers 3.1 to 3.5 were tested.

p0099A hammer according to DIN 1041 (weight without handle: 800 g, length: 35 cm) was used to carry out the steel wool scratch test. The test panels were stored for 24 hours at room temperature prior to the test.

p0100The flat side of the hammock was covered with a layer of steel wool, and fixed with tescrep on the raised sides. The hammer was placed at right angles to the clear lacquers. The weight of the hammer was guided over the surface of the clear lacquer without any over-stressed and without additional physical force.

p010110 double strokes were performed by hand during each test. After each of these individual tests, the steel wool was replaced.

p0102After the load, the test surfaces were cleaned with a soft cloth from the steel wool tests. The test areas were evaluated visually under artificial light and graded as follows:

Note impairment

p0103<ol><li>1 does not exist</li><li>2 low</li><li>3 moderately</li><li>4 moderate to medium</li><li>5 strong</li><li>6 very strong</li></ol>

p0104The evaluation took place immediately after the end of the experiment.

p0105Table 2 gives an overview of the results. They underline that the clear lacquers 3.1 to 3.5 were hard, flexible and highly scratch-resistant.<tables id="tabl0002" num="0002"><table frame="bottom"><title><b>TABLE 2 The hardness, flexibility and scratch resistance of the clear lacquers 3.1 to 3.5</b></title><tgroup cols="6" colsep="0"><colspec colnum="1" colname="col1" colwidth="55mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="18mm" /><colspec colnum="6" colname="col6" colwidth="18mm" /><thead><row><entry valign="top"><b>test</b></entry><entry namest="col2" nameend="col6" align="left" valign="top"><b>Clear lacquer:</b></entry></row><row><entry valign="top" /><entry valign="top"><b>3.1</b></entry><entry valign="top"><b>3.2</b></entry><entry valign="top"><b>3.3</b></entry><entry valign="top"><b>3.4</b></entry><entry valign="top"><b>3.5</b></entry></row></thead><tbody><row><entry valign="bottom">Universal hardness at 25.6 mN [N / mm²]</entry><entry valign="bottom">92</entry><entry valign="bottom">79.2</entry><entry valign="bottom">77.8</entry><entry valign="bottom">77.8</entry><entry valign="bottom">92</entry></row><row><entry valign="bottom">relative elastic</entry><entry valign="bottom" /><entry valign="bottom" /><entry valign="bottom" /><entry valign="bottom" /><entry valign="bottom" /></row><row><entry valign="bottom">Deep rebound (%)</entry><entry valign="bottom">62.4</entry><entry valign="bottom">60.2</entry><entry valign="bottom">61.7</entry><entry valign="bottom">61.7</entry><entry valign="bottom">62.4</entry></row><row><entry valign="bottom">Steel wool scratch test (Note)</entry><entry valign="bottom">1-2</entry><entry valign="bottom">1-2</entry><entry valign="bottom">1-2</entry><entry valign="bottom">1-2</entry><entry valign="bottom">1-2</entry></row></tbody></tgroup></table></tables>

Example 4

The preparation of the clear lacquers 4.1 to 4.5 and the clear lacquers 4.1 to 4.5

p0106The 10% strength by weight solution of nanoparticles according to Preparation Example 1 and water were introduced into a round flask equipped with a magnetic stirrer. The methacrylate copolymer (A2) according to Example 2 was added to the initial charge while stirring. The resulting reaction mixture was stirred at room temperature for one hour. Then, isopropanol was added and the resulting reaction mixture was stirred at room temperature for four hours. The milky cloudy reaction mixture cleared and a translucent clear lacquer formed.

p0107Table 3 gives an overview of the material composition of the clear lacquers 4.1 to 4.5 produced according to this general preparation specification. They were easy to transport and storage stable.<tables id="tabl0003" num="0003"><table frame="bottom"><title><b>Table 3: The material composition of clear lacquers 4.1 to 4.5</b></title><tgroup cols="6" colsep="0"><colspec colnum="1" colname="col1" colwidth="90mm" /><colspec colnum="2" colname="col2" colwidth="13mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><colspec colnum="4" colname="col4" colwidth="13mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><thead><row><entry valign="top"><b>component</b></entry><entry namest="col2" nameend="col6" align="left" valign="top"><b>Weights in clear lacquer:</b></entry></row><row><entry valign="top" /><entry valign="top"><b>4.1</b></entry><entry valign="top"><b>4.2</b></entry><entry valign="top"><b>4.3</b></entry><entry valign="top"><b>4.4</b></entry><entry valign="top"><b>4.5</b></entry></row></thead><tbody><row><entry valign="bottom">Nanoparticle solution according to Preparation Example 1</entry><entry valign="bottom">1</entry><entry valign="bottom">1</entry><entry valign="bottom">1</entry><entry valign="bottom">1</entry><entry valign="bottom">1</entry></row><row><entry valign="bottom">Solution of the methacrylate copolymer (A2) according to Example 2</entry><entry valign="bottom">3</entry><entry valign="bottom">3.5</entry><entry valign="bottom">4</entry><entry valign="bottom">4,5</entry><entry valign="bottom">5</entry></row><row><entry valign="bottom">water</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry></row><row><entry valign="bottom">isopropanol</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry><entry valign="bottom">1.58</entry></row></tbody></tgroup></table></tables>

p0108The clear lacquers 4.1 to 4.5 were applied pneumatically by means of flow-gun guns to steel plates, which were pre-lacquered in the order listed above with electrocoat coating, a filler lacquer and a black water base lacquer. The wet layer thickness of the applied clearcoat layers 4.1 to 4.5 was selected in such a way that the cured clearcoats 4.1 to 4.5 had a dry layer thickness of 20 μm. The applied clearcoat layers 4.1 to 4.5 were flashed off at room temperature for 10 minutes and thermally cured at 140 ° C. for 22 minutes. Heraeus recirculating furnaces were used for thermal curing.

p0109High-gloss, clear clear lacquers 4.1 to 4.5 were obtained, which had a very good flow and were free from stress cracks and surface defects such as cratering. The scratch resistance according to the steel wool scratch test and the chemical stability according to BART of the clear lacquers 4.1 to 4.5 were examined.

p0110The BART (BASF ACID RESISTANCE TEST) was used to determine the resistance of a clear lacquer against acids, alkalis and water droplets. The clear lacquer coating on a gradient oven was subjected to a temperature load for 30 minutes at 40 ° C. after the baking. Prior to this, the test substances (sulfuric acid 10%, 36% sulphurous acid 6%, hydrochloric acid 10%, sodium hydroxide solution 5%, deionized water 1.2, 3 or 4 drops) defined with a dosing pipette. Following the action of the substances, these were removed under running water and the damage was visually assessed after 24 h according to a predetermined scale:<tables id="tabl0004" num="0004"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="89mm" /><thead><row><entry valign="top"><b>mark</b></entry><entry valign="top"><b>Appearance</b></entry></row></thead><tbody><row><entry>0</entry><entry>no defect</entry></row><row><entry>1</entry><entry>easy marking</entry></row><row><entry>2</entry><entry>Marking / tiling / no softening</entry></row><row><entry>3</entry><entry>Marking / Masking / Hue Change / Softening</entry></row><row><entry>4</entry><entry>Cracks / beginning of etching</entry></row><row><entry>5</entry><entry>Clear lacquer removed</entry></row></tbody></tgroup></table></tables>

p0111Each individual marker (spot) was evaluated and the result was recorded in the form of a note for each test substance.

p0112Table 4 gives an overview of the results. They underlined that the clear lacquers 4.1 to 4.5 were resistant to chemicals and highly scratch-resistant.<tables id="tabl0005" num="0005"><table frame="bottom"><title><b>Table 4: Chemical stability and scratch resistance of the clear lacquers 4.1 to 4.5</b></title><tgroup cols="6" colsep="0"><colspec colnum="1" colname="col1" colwidth="42mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="20mm" /><thead><row><entry valign="top"><b>test</b></entry><entry namest="col2" nameend="col6" align="left" valign="top"><b>Clear lacquer:</b></entry></row><row><entry valign="top" /><entry valign="top"><b>4.1</b></entry><entry valign="top"><b>4.2</b></entry><entry valign="top"><b>4.3</b></entry><entry valign="top"><b>4.4</b></entry><entry valign="top"><b>4.5</b></entry></row></thead><tbody><row><entry>Steel wool scratch test (Note)</entry><entry>1-2</entry><entry>1-2</entry><entry>1-2</entry><entry>1-2</entry><entry>2</entry></row><row><entry>BEARD</entry></row><row><entry>Sulfuric acid 10%</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry></row><row><entry>Sulfuric acid 36%</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry></row><row><entry>Hydrochloric acid 10%</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>1</entry></row><row><entry>Sulphurous acid 6%</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry></row><row><entry>Sodium hydroxide solution 5%</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry></row><row><entry>VE water</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry><entry>0</entry></row></tbody></tgroup></table></tables>

Example 5

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

p01131,502.7 parts by weight of the methacrylate copolymer (A1) of Example 1, 2,693.7 parts by weight of isopropanol and 365.4 parts by weight of 0.1 N acetic acid were initially taken in a round glass flask equipped with a stirrer, reflux condenser, thermometer and external heating and the mixture was stirred for 3 hours With stirring to 70 ° C. Subsequently, 1,394.4 parts by weight of Solventnaphtha® were added, after which the resulting reaction mixture was stirred at 70 ° C. for a further five minutes. The low-boiling constituents, in particular the water, were then distilled off in vacuo at 70 ° C. (3,737.9 parts by weight), and 2,218.3 parts by weight of the condensate were obtained. The residual contents of water (0.2% by weight) and isopropanol (2.5% by weight) were determined by gas chromatography. The condensate was storage stable at 40 ° C for more than four weeks. It was excellently suited for the production of clear lacquers.

Example 6

The preparation of the two-component clear lacquers 6.1 and 6.2 and the clear lacquers 6.1 and 6.2

p0114To produce the two-component clear lacquer 6.1, 100 parts by weight of the condensate from Example 5, 20 parts by weight of Decanol® EX-252 (commercial product from Nagase Chemtex Corporation, Osaka, Japan) and 1 part by weight of a commercial leveling agent (Byk® 301 from Byk Chemie) were mixed .

p0115To produce the two-component clear lacquer 6.2, 30 parts by weight of Decanol® EX-252 were used instead of 20 parts by weight.

p01169.7 parts by weight of the catalyst of Preparation Example 1 were added to the resulting mixtures 6.1 and 6.2. The resulting two-component clear lacquers 6.1 and 6.2 were applied pneumatically with flow-gun guns to steel sheets, which were pre-lacquered in the order indicated one above the other with electrocoat coating, a filler lacquer and a black water base lacquer. The wet layer thickness of the applied clearcoat layers 6.1 and 6.2 was chosen in such a way that the hardened clearcoats 6.1 and 6.2 had a dry layer thickness of 40 μm. The applied clearcoat layers 6.1 and 6.2 were vented for 10 minutes at room temperature, dried for 5 minutes at 60 ° C. and thermally cured at 140 ° C. for 22 minutes. Heraeus recirculating furnaces were used for thermal curing.

p0117The scratch resistance of the clear paints 6.1 and 6.2 was determined by means of the wash road test according to AMTEC. Their chemical reliability was determined by means of the gradient oven test. The results are shown in Table 5. They support the high scratch resistance and chemical stability of the clear lacquers 6.1 and 6.2.<tables id="tabl0006" num="0006"><table frame="bottom"><title><b>Table 5: Scratch resistance and chemical stability of clear lacquers 6.1 and 6.2</b></title><tgroup cols="3" colsep="0"><colspec colnum="1" colname="col1" colwidth="67mm" /><colspec colnum="2" colname="col2" colwidth="39mm" /><colspec colnum="3" colname="col3" colwidth="39mm" /><thead><row><entry valign="top"><b>test</b></entry><entry namest="col2" nameend="col3" align="left" valign="top"><b>Clear lacquer:</b></entry></row><row><entry valign="top" /><entry valign="top"><b>6.1</b></entry><entry valign="top"><b>6.2</b></entry></row><row><entry valign="top"><u>Gradient oven test</u>:</entry><entry valign="top" /><entry valign="top" /></row></thead><tbody><row><entry>Start of injury after 24 hours (° C)</entry></row><row><entry>Sodium hydroxide solution</entry><entry>42</entry><entry>> 75</entry></row><row><entry>sulfuric acid</entry><entry>46</entry><entry>47</entry></row><row><entry>distilled water</entry><entry>> 75</entry><entry>> 75</entry></row><row><entry>pancreatin</entry><entry>55</entry><entry>60</entry></row><row><entry>tree resin</entry><entry>> 75</entry><entry>> 75</entry></row><row><entry><u>AMTEC</u>:</entry></row><row><entry>Gloss at 20 ° according to DIN 67530 (units):</entry></row><row><entry>Initial luster</entry><entry>83</entry><entry>84</entry></row><row><entry>Gloss after damage:</entry></row><row><entry>without cleaning</entry><entry>54</entry><entry>50</entry></row><row><entry>with cleaning</entry><entry>64</entry><entry>76</entry></row><row><entry>Residual luster (%)</entry><entry>77</entry><entry>80</entry></row></tbody></tgroup></table></tables>