WO2003022937A1 - Polysiloxane sols which can be thermally cured and cured by actinic radiation, method for the production and use thereof - Google Patents

Abstract

The invention relates to polysiloxane sols (dual cure polysiloxane sols) which can be produced by hydrolysis and condensation (A) of at least one hydrolysable silicon compound of general formula (I) XmSi(R-Yn)4-m (I), wherein the indices and variables have the following meaning: m: 1, 2 or 3; n: 1, 2 or 3; X: a hydrolysable radical; R: a non-hydrolysable divalent organical radical; Y: a blocked isocyanate group, in the presence of (B) at least one compound containing at least one reactive functional group having at least one bond which can be activated by actinic radiation and at least one isocyanate-reactive functional group. The invention also relates to a method for the production and the use thereof as coating materials, adhesives and sealing materials, or to the production thereof.

Description

Polysiloxane brines curable thermally and with actinic radiation, process for their preparation and their use

The present invention relates to novel thermally curable and actinic radiation polysiloxane brines. In addition, the present invention relates to a new process for the preparation of thermally and actinic radiation-curable polysiloxane sols. Furthermore, the present invention relates to the use of the new thermally and actinic radiation-curable polysiloxane sols as coating materials, adhesives and sealants or as constituents of thermally curable and actinic radiation coating materials, adhesives and sealants.

Here and below, actinic radiation includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, or

Understand corpuscular radiation, such as electron radiation. The joint curing of coating materials, adhesives and sealants with heat and actinic radiation is also referred to by experts as dual-cure.

Polysiloxane brine (dual-cure polysiloxane brine) curable thermally and with actinic radiation has long been known. For example, they are sold under the brand Ormocer ® (organically modified ceramic) and are used to produce comparatively thin, scratch-resistant coatings.

For example, German patent application DE 199 10 876

A 1 shows a coating with a thickness of 2 to 18 μm, which is produced by the hydrolysis and condensation of a coating material with 20 to 100 Mol%, based on the monomeric starting components, of a hydrolyzable silicon compound of the general formula I.

X _m SiR. _m -Y _n (I),

will be produced. In the general formula I, X denotes a fine hydrolyzable radical. R stands for a non-hydrolyzable divalent organic radical and Y stands for a blocked isocyanate group. The indices m and n independently of one another represent 1, 2 or 3. The hydrolyzable silicon compound I can be crosslinked not only via the hydrolysis and condensation of the radicals X, but also via the blocked isocyanate groups with compounds which contain isocyanate-reactive groups. The coating materials can be cured by heat treatment and / or by treatment with radiation, preferably IR, electron radiation, UV or microwaves.

The hydrolysis and condensation of the hydrolyzable silicon compound I in the presence of compounds which contain at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group does not emerge from the German patent application. In addition, the use of the known coating material for modifying known dual-cure coating materials is not described.

German patent application DE 38 36 815 A 1 describes a process for producing scratch-resistant coatings by hydrolysis and condensation of at least one silicon compound of the general formula R _m S 1X ₄ . • ₁ m

known. Here R stands for a non-hydrolyzable radical which can also contain, inter alia, olefinically unsaturated double bonds. The radical X stands for a hydrolyzable radical. The known coating materials also contain at least one polyfunctional organic compound with activatable functional groups. These compounds are preferably blocked polyisocyanates and polyesters.

The hydrolysis and condensation of the hydrolyzable silicon compound in the presence of compounds which contain at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group is not apparent from the German patent application. In addition, the use of the known coating material for modifying known dual-cure coating materials is not described.

A method for imagewise coating of substrates is known from European patent application EP 0 365 027 A 2. A coating material is used which, by hydrolysis and condensation of 25 to 100 mol% of at least one silicon compound of the formula

R'SiR,

can be produced. Herein R 'denotes a group which is stable to hydrolysis and is polymerisable thermally and / or with actinic radiation and R is a hydrolyzable group. The polymerisable groups are Residues containing epoxy groups and / or carbon-carbon double bonds are used.

Compounds which are also amenable to polymerization can also be added to the coating materials. Reactive (meth) acrylate monomers such as dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylol propane diacrylate,

Pentaerythritol triacrylate, pentaerythritol tetraacrylate, urethane dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate and the corresponding prepolymers, listed and placed side by side as equivalent. This means that trimethylol propane diacrylate and pentaerythritol triacrylate, which contain 2 or 3 reactive functional groups with a bond which can be activated with actinic radiation and an isocyanate-reactive hydroxyl group, are not considered to have any particular technical effect.

After the application of the known coating material to a substrate, the resulting wet layer is hardened by point heating or by imagewise exposure, after which the non-hardened areas are removed with the aid of solvents and / or dilute alkalis.

The use of the known coating materials for the modification of known dual-cure coating materials is not described in the European patent application.

A method for coating plastic substrates is known from European patent application EP 0 450 625 A1, in which a coating material is used which is produced by hydrolysis and condensation of hydrolyzable silicon compound. The hydrolyzable silicon compound contains 1 to 40 mol% of non-hydrolyzable groups, the ethylenically unsaturated bonds exhibit. In addition, they contain silicon compound with non-hydrolyzable groups that have a mercapto residue. The applied coating materials are hardened with actinic radiation and, if necessary, thermally hardened. Alternatively, they can only be thermally hardened.

The German patent application does not disclose the hydrolysis and condensation of the hydrolyzable silicon compounds in the presence of compounds which contain at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group. In addition, the use of the known coating material for modifying known dual-cure coating materials is not described.

The well-known dual-cure coating materials based on hydrolyzable polysiloxane sols provide scratch-resistant coatings. The adhesion of the coatings to the substrates often leaves something to be desired. In addition, because of the comparatively low solids content of the known dual-cure coating materials, it is not possible or only with comparatively great effort to produce coatings with a layer thickness> 10 μm. It is therefore also difficult and technically complex to equip large substrates, such as painted automobile bodies, with the known dual-cure coating materials based on hydrolyzable polysiloxane sols to make them scratch-resistant.

Thermally curable coating materials based on hydroxyl-containing polyesters and blocked polyisocyanates are known from European patent application EP 0 872 500 A1, which are scratch-resistant

Deliver coatings with a layer thickness of 20 to 40 μm. The Blocked polyisocyanates are made by reacting a silane, such as diethyl N- (3-trimethoxysilylpropyl) aspartate, with colloidal metal oxides. The reaction can also be carried out in the presence of siloxanes containing vinyl and allyl groups. However, these compounds are mentioned in one breath with numerous other siloxanes that contain no vinyl and allyl groups, and no possible dual cure is indicated. The known coating materials are therefore only thermally crosslinked.

Dual-cure coating materials, in particular dual-cure clearcoats, which contain components which are curable thermally and / or with actinic radiation, such as binders, crosslinking agents and, if appropriate, reactive diluents, are known, for example, from German patent applications DE 198 18 735 A1, DE 199 08 013 A1, DE 199 08 018 A1, DE 199 20 799 A1 or DE 199 20 801 A1, the European patent application EP 0 928 800 A1 or the international patent application WO 98/40170.

The previously known dual-cure clearcoats and the coatings produced from them have a very advantageous profile of properties that must be maintained.

However, the known dual-cure clearcoats show certain weaknesses in the continuous painting process, such as is carried out in continuous operation in the painting system of a motor vehicle factory. In these painting systems, the applied dual-cure clear coats are first dried and thermally hardened on the bodies at high temperatures, after which they are hardened with UV radiation immediately without any significant cooling. Since the bodies represent complex three-dimensional substrates, they have numerous shadow zones, such as cavities, folds and other design-related undercuts or edges. However, the optimal, in particular complete, illumination of the shadow zones with UV radiation is very complex and time-consuming in terms of equipment and control technology, because point, small-area and omnidirectional spotlights, combined with automatic movement devices, must also be used here.

However, if optimal illumination is dispensed with, it has hitherto had to be accepted that the resulting coatings or paints in the shadow zones have an unsatisfactory application-related property profile. In particular, they do not achieve the scratch resistance and chemical resistance of the fully hardened coatings or paintwork outside the shadow zones. This can cause problems not only in the later use of the motor vehicles, but also in the further painting process in the painting system and in the further manufacturing process, for example when installing seats, doors, windows, electrical parts and motors in the painted bodies. This can easily damage the paintwork due to mechanical and chemical effects.

The problems described above also occur with the dual-cure sealing compounds and adhesives of the prior art and the seals and adhesive layers produced therefrom.

In the unpublished German patent application DE 100 41 635.7 a dual-cure coating material is described which (A) at least one crosslinking agent containing, on average, at least one blocked isocyanate group and at least one functional group with at least one bond which can be activated with actinic radiation in the molecule, and

(B) at least one binder with an average of at least one isocyanate-reactive functional group

contains. In addition, the dual-cure coating material can contain a wide variety of additives; However, no mention is made of polysiloxane brine.

It is an object of the present invention to provide new polysiloxane sols (dual-cure polysiloxane sols) curable thermally and with actinic radiation which can be prepared by hydrolysis and condensation of at least one hydrolyzable silicon compound and which, as such, are dual-cure coating materials, - Adhesives and sealants can be used to produce highly scratch-resistant coatings, adhesive layers and seals. The new dual-cure polysiloxane brine should be able to be produced and stored at room temperature.

In particular, however, the new dual-cure polysiloxane sols should be usable as constituents of known dual-cure coating materials, adhesives and sealants, in particular dual-cure clearcoats. They should not cause cloudiness in the new dual-cure coating materials, adhesives and sealants, but should be homogeneously distributable.

Furthermore, the new dual-cure coating materials, especially the new dual-cure clearcoats, should be without any special technical effort Deliver coatings, especially clear coats, with a high layer thickness, which is necessary and advantageous for their technical function. The new clearcoats in particular should have a high gloss, high clarity, high resistance to condensation, excellent interlayer adhesion, high hardness even in the shadow areas of substrates, high scratch resistance and very good weather resistance and chemical resistance.

Accordingly, the new thermally and actinic radiation-curable polysiloxane sols have been found by hydrolysis and condensation

(A) at least one hydrolyzable silicon compound of the general formula I:

X _m Si (RY _n ) ₄ - _m (I),

where the indices and the variables have the following meaning:

m 1, 2 or 3;

n 1, 2 or 3;

X hydrolyzable residue;

R non-hydrolyzable divalent organic residue;

Y blocked isocyanate group;

in the presence of (B) at least one compound containing at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group;

are producible.

In the following, the new polysiloxane brines curable thermally and with actinic radiation are referred to as "brine according to the invention" for the sake of brevity.

In addition, the new process for the production of thermally and actinic radiation-curable polysiloxane sols by hydrolysis and condensation

(A) at least one hydrolyzable silicon compound of the general formula I:

X _m Si (RY _n ) ₄ . _m (I),

where the indices and the variables have the following meaning:

m 1, 2 or 3;

n 1, 2 or 3;

X hydrolyzable residue;

R non-hydrolyzable divalent organic residue;

Y blocked isocyanate group; in the presence of

(B) at least one compound containing at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group;

found.

For the sake of brevity, the new process for the preparation of polysiloxane brines which are curable thermally and with actinic radiation is referred to below as the “process according to the invention”.

Furthermore, the new use of the brine according to the invention as dual-cure coating materials, adhesives and sealants for the production of highly scratch-resistant coatings, adhesive layers and seals was found.

Last but not least, the new use of the brine according to the invention as a component of dual-cure coating materials, adhesives and sealing compounds, in particular of dual-cure clearcoats, for the production of coatings, adhesive layers and seals, in particular clearcoats, has been found.

Further subjects of the invention are evident from the description.

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

The person skilled in the art could not have foreseen that the object on which the present invention was based could be achieved with the aid of the brine according to the invention. It was particularly surprising that the inventive Brine could be produced and stored at room temperature, which is a great advantage in terms of logistics, equipment, process technology and safety.

In particular, because of the different material composition, it was not to be expected that the brine according to the invention could be easily incorporated into known dual-cure coating materials, adhesives and sealants without clouding or precipitation of constituents. This made it possible, in particular, to produce new dual-cure clearcoats in which cloudiness would have made it impossible to use them to produce high-quality clearcoats from the outset.

It was also surprising that the dual-cure clearcoats according to the invention also provided hard and scratch-resistant clearcoats in the shadow zones of complexly shaped substrates, such as motor vehicle bodies, which were no longer so easily damaged in the line in the further manufacturing process of the motor vehicles concerned.

Overall, the extraordinarily broad applicability of the brine according to the invention, which spanned pigmented and unpigmented dual-cure coating materials, pigmented and unpigmented adhesives, and pigmented and unpigmented sealants, was surprising.

The sols according to the invention can be prepared by hydrolysis and condensation of at least one hydrolyzable silicon compound (A) of the general formula I: X _m Si (RY _n ) ₄ . _m (l).

In the general formula I, the index m stands for 1, 2 or 3, in particular 1.

Regardless of this, the index n stands for 1, 2 or 3, in particular 1.

The radical R represents a non-hydrolyzable, double-bonded organic radical. The radical R is preferably selected from the group consisting of double-bonded radicals which are derived from at least one of the following organic compounds:

(i) Substituted and unsubstituted, none or at least one

Heteroatom in the chain and / or in the ring containing linear or branched alkanes, alkenes, cycloalkanes, cycloalkenes,

Alkylcycloalkanes, alkylcycloalkenes, alkenylcycloalkanes or

alkenylcycloalkenes;

(ii) substituted and unsubstituted aromatics or heteroamates; such as

(iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl,

Alkylcycloalkenyl-, alkenylcycloalkyl- or alkenylcycloalkenyl-substituted aromatics or heteroaromatics, the substituents of which are substituted or unsubstituted and none or at least one

Contain heteroatom in their chain and / or ring;

selected.

Examples of suitable heteroatoms are oxygen, nitrogen, boron, silicon, sulfur or phosphorus atoms. Examples of suitable substituents for the abovementioned radicals R are halogen atoms, in particular fluorine and chlorine atoms, nitro groups or nitrile groups, and the substituents described in German patent application DE 199 10 876 A1, page 2, lines 42 to 45.

Examples of suitable aromatics are benzene and naphthalene.

Examples of suitable heteroaromatics are thiophene, pyridine or triazine.

Examples of suitable alkanes are those with 2 to 20 carbon atoms in the molecule, such as ethane, propane, butane, isobutane, pentane, neopentane, hexane, heptane, octane, isooctane, nonane, dodecane, hexadecane or eicosane.

Examples of suitable alkenes are ethylene and propylene.

Examples of suitable cycloalkanes are cyclopentane and cyclohexane.

Examples of suitable cycloalkenes are cyclopentene and cyclohexene.

Examples of suitable alkylcycloalkanes are methylcyclopentane and methylcyclohexane.

Examples of suitable alkylcycloalkenes are methylcyclopentene and methylcyclohexene.

Examples of suitable alkenylcycloalkanes are allyl and vinylcyclopentane and allyl and vinylcyclohexane.

Examples of suitable alkenylcycloalkenes are vinylcyclopentene and vinylcyclohexene. Examples of suitable alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or

Alkenylcycloalkenyl substituents are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, cyclohexyl, cyclohexenyi, 4-methylcyclohexyl, 4-methylcyclohexenyl, 3-allylcyclohexenyl or 4-vinylcyclohexenyl.

Further examples of suitable radicals R are known from German patent application DE 199 10 876 A1, page 2, lines 40 to 42.

The radicals R are preferably derived from organic compounds which are unsubstituted as such or whose substituents are unsubstituted.

Advantageously, these compounds also do not contain heteroatoms in their chains and / or in their rings and / or in the chains and / or the rings of their substitutes.

Particular advantages result if the radicals R are derived from linear alkanes which meet the advantageous conditions mentioned above. Further advantages result if they are derived from ethane, propane, butane, pentane or hexa, in particular propane.

The radicals Y are blocked isocyanate groups.

A customary and known blocking agent can be used as the blocking agent for producing the blocked isocyanate groups. The blocking agents are preferably selected from the group consisting of (i) phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, tert-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;

(ii) lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or ß-propiolactam;

(iii) active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;

(iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether,

Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,

Diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylol urea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1, 3-

Dichloro-2-propanol, 1, 4-cyclohexyldimethanol or

acetone cyanohydrin;

(v) mercaptans, such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole,

Thiophenol, methylthiophenol or ethylthiophenol;

(vi) acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;

(vii) imides such as succinimide, phthalimide or maleimide; (viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;

(ix) imidazoles such as imidazole or 2-ethylimidazole;

(x) ureas, such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenyl urea;

(xi) carbamates, such as phenyl N-phenylcarbamate or 2-

oxazolidone;

(xii) imines such as ethyleneimine;

(xiii) oximes, such as acetone oxime, formal doxime, acetaldoxime, acetoxime,

Methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime,

Benzophenone oxime or chlorohexanone oximes;

(xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;

(xv) hydroxamic sauce esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or

(xvi) substituted pyrazoles and triazoles; such as

(xvii) mixtures of these blocking agents;

selected. Substituted pyrazoles, such as those from European patent application EP 0 159 117 A1, are preferred are known, and triazoles, such as 1, 2,4-triazole, and mixtures of substituted pyrazoles and triazoles are used.

The radicals X of the general formula I are monovalent hydrolyzable radicals.

The radicals X are preferably selected from the group consisting of hydrogen atoms and halogen atoms, hydroxyl groups and primary and secondary amino groups, and substituted and unsubstituted alkoxy, cycloalkoxy, aryloxy, acyloxy, alkoxycarbonyl, cycloalkoxycarbonyl and aryloxycarbonyl groups. The hydrolyzable radicals X from the group of alkoxy groups having 1 to 4 carbon atoms in the alkylene radical, in particular methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, tert-butoxy and sec.-butoxy groups, are preferred, specifically methoxy and ethoxy groups.

Examples of particularly advantageous hydrolyzable silicon compounds (A) to be used according to the invention are 3-isocyanatopropyl-trimethoxysilane -triethoxysilane, -dimethoxy-ethoxysilane, -methoxy-diethoxysilane, di- (3-isocyanatopropyl) -dimethoxysilane, -diethoxysilane and -diethoxysilane -ethoxysilane and tris- (3-isocyanatopropyl) -methoxysilane and - ethoxysilane, in particular 3-isocyanatopropyl-triethoxysilane, which were blocked with a stoichiometric amount of the blocking agents described above.

The amount of hydrolyzable silicon compounds (A) which is used to produce the brine according to the invention by the process according to the invention can vary widely and depends on the requirements of the individual case. The hydrolyzable silicon compounds (A) are preferably used in an amount of 1 to 50, preferably 2 to 45, particularly preferably 3 to 40, very particularly preferably 4 to 35 and in particular 5 to 30% by weight, in each case based on the total amount of the starting products.

According to the invention, the hydrolyzable silicon compounds (A) of the general formula I described above are present in the presence of at least one compound (B)

(i) at least one, preferably at least two, particularly preferably at least three, very particularly preferably at least four and in particular five reactive functional groups

Group (s) with at least one, in particular one, bond which can be activated with actinic radiation and

(ii) at least one, in particular one, isocyanate-reactive functional group,

hydrolyzed and condensed.

In the process according to the invention, they can be added to the hydrolyzable silicon compounds (A) before, during and / or after, in particular before, the hydrolysis and condensation.

Examples of suitable bonds which can be activated with actinic radiation are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the double bonds, especially the carbon-carbon double bonds

("Double bonds"), preferably used. Suitable double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups. Of these, (meth) acrylate groups are particularly advantageous and are therefore used with very particular preference.

Examples of suitable isocyanate-reactive functional groups are thiol groups, hydroxyl groups and primary and secondary amino groups, especially hydroxyl groups.

Examples of suitable compounds (B) are known from German patent application DE 198 18 735 A1, column 2, lines 24 to 36, column 3, line 16 to column 6, line 33, and column 6, lines 34 to 68. Well-suited examples are pentaerythritol triacrylate, which is sold under the trademark Sartomer ® 444 D by Cray Valley, France, and dipentaerythritol pentaacrylate, which is sold under the trademark Sartomer ® 399 by the same company.

The content of the compounds (B) in the brine according to the invention can likewise vary widely and depends on the requirements of the individual case. The compounds (B) are preferably used in an amount of 1 to 60, preferably 2 to 50, particularly preferably 3 to 40, very particularly preferably 5 to 35 and in particular 10 to 30% by weight, in each case based on the total amount of the starting products, used. In the hydrolysis and condensation, at least one of the compounds (C) to (G) described below can also be present as the starting product.

For example, in the process according to the invention, the hydrolysis and condensation in the presence of at least one hydrolyzable silicon compound (C) of the general formula II:

X _m Si (RZ _n ) ₄ . _m (II),

wherein the indices m and n and the variables X and R have the meanings given above, are carried out.

In the general formula II, Z stands for one of the isocyanate-reactive functional groups described above, in particular an amino group, one of the reactive functional groups described above with at least one bond which can be activated with actinic radiation and / or an epoxy group.

Examples of suitable hydrolyzable silicon compounds (C) of the general formula II are from German patent application DE 199 10 876 A1, page 2, line 56, to page 3, line 2, and European patent application EP 0 450 625 A1, page 3, line 42, to page 4, line 9, European patent application EP 0 365 027 A 2, page 3, lines 16 to 31, German patent application DE 38 36 815 A 1, page 2, line 57, to page 3, line 31, or the European patent application EP 0 872 500 A1, page 4, lines 37 to 49.

3-Aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane and glycidoxypropyltrimethoxysilane are particularly suitable. If used, the amount of hydrolyzable silicon compounds (C) of the general formula II which is used for the production of the brine according to the invention by the process according to the invention can vary widely and depends on the requirements of the individual case. The hydrolyzable silicon compounds (C) are preferably used in an amount of 1 to 45, preferably 2 to 40, particularly preferably 3 to 35, very particularly preferably 4 to 30 and in particular 5 to 25% by weight, in each case based on the total amount of the starting products , used.

The hydrolysis and condensation can furthermore be carried out in the presence of at least one hydrolyzable silicon compound (D) of the general formula III:

X _p SiR ^' ₄ .p (III),

wherein the index p = 1, 2, 3 or 4, in particular 2, 3 or 4, X means at least one of the hydrolyzable radicals X described above and R ^'is a monovalent, non-hydrolyzable radical which is different from at least one of the above the radicals R described organic compounds.

Examples of suitable hydrolyzable silicon compounds (D) are methyltriethoxysilane, methyltrimethoxysilane, tetramethylorthosilicate, tetraethylorthosilicate, dimethyl, diethyl, dipropyl, methylethyl, methylpropyl and ethylpropyldimethoxysilane, dimethyl, diethyl, methyl, dipropyl, dipropyl Ethylpropyldiethoxysilane, dimethyl, diethyl, dipropyl, methylethyl, methylpropyl and

Ethyl propyl dipropoxysilane, dimethyl, diethyl, dipropyl, methyl ethyl, methyl propyl and ethyl propyl methoxy ethoxysilane, dimethyl, diethyl, dipropyl, methyl ethyl, methyl propyl and ethyl propyl methoxypropoxysilane as well as dimethyl, diethyl, dipropyl, methylethyl, methylpropyl and ethylpropylethoxypropoxysilane. Further examples are known from European patent application EP 0 872 500 A1, page 4, lines 37 to 49.

If used, the amount of hydrolyzable silicon compounds (D) of the general formula III which is used for the production of the brine according to the invention by the process according to the invention can vary widely and depends on the requirements of the individual case. The hydrolyzable silicon compounds (D) are preferably used in an amount of 0.1 to 20, preferably 0.2 to 18, particularly preferably 0.3 to 15, very particularly preferably 0.4 to 12 and in particular 0.5 to 10% by weight. -%, based in each case on the total amount of the starting products.

The hydrolysis and condensation can also be carried out in the presence of at least one hydrolyzable metal compound (E) of the general formula IV:

X _p MRVp (IV),

where the indices p and r are an integer between 1 and 4, with the proviso that p + r = 2, 3 or 4, in particular 3 or 4, M for tin, boron, aluminum, titanium or zirconium, in particular aluminum, X is at least one of the hydrolyzable radicals X described above and R ^'is a monovalent, non-hydrolyzable radical which is derived from at least one of the organic compounds described above for the R radicals.

Examples of suitable hydrolyzable metal compounds (E) of the general formula IV are, for example, from the European one Patent application EP 0 450 625 A1, page 4, line 47, to page 5, line 32, is known, the vanadinyl compounds mentioned there being able to be used instead of or in addition to the hydrolyzable metal compounds (E).

Aluminum tri-sec-butoxide is particularly preferably used.

If used, the amount of hydrolyzable metal compounds (E) of the general formula IV which is used for the production of the brine according to the invention by the process according to the invention can vary widely and depends on the requirements of the individual case. The hydrolyzable metal compounds (E) are preferably used in an amount of 1 to 25, preferably 2 to 22, particularly preferably 3 to 20, very particularly preferably 4 to 18 and in particular 5 to 15% by weight, in each case based on the total amount of the starting products , used.

In addition, the hydrolysis and condensation can be carried out in the presence of at least one organic thio compound (F) of the general formula V:

S (RZ _n ) ₂ (V),,

where the index n and the variable Z have the meaning given above.

Examples of particularly suitable organic thio compounds (F) are bis (6-hydroxyhexyl), bis (5-hydroxypentyl), bis (4-hydroxybutyl), bis (3-hydroxypropyl) and bis ( 2-hydroxyethyl) sulfide (thiodiethanol). If used, the amount of organic thio compounds (F) of the general formula IV which are used for the production of the brine according to the invention by the process according to the invention can vary widely and is based on the requirements of the individual case.

In the process according to the invention, the hydrolysis and condensation can be accompanied by complexation. The complexing agents (G) are selected from the group of organic compounds which form chelate ligands. These are preferably non-aromatic organic compounds. The organic compounds (G) contain at least two functional groups which can coordinate with metal atoms or ions. These functional groups are usually electron donors which donate electrons to metal atoms or ions as electron acceptors. In principle, all organic compounds (G) of the type mentioned are suitable for the process according to the invention, as long as they do not adversely affect or even completely prevent the hydrolysis and condensation and / or the crosslinking to the finished coating. Examples of suitable organic compounds (G) are dimethylglyoxime or compounds which contain carbonyl groups in the 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 634.

If used, the amount of complexing agents (G) which is used for the production of the brine according to the invention by the process according to the invention can vary widely and depends on the requirements of the individual case. The complexing agents (G) are preferably used in an amount of 1 to 25, preferably 2 to 22, particularly preferably 3 to 20, very particularly preferably 4 to 18 and in particular 5 to 15% by weight, based in each case on the total amount of the starting products.

The hydrolysis and condensation and optionally the complexation of the starting products described above can optionally be carried out in the presence of solvents, preferably aromatics-free solvents. It is preferably carried out without solvents. The starting products described above are preferably initially introduced and homogenized. The amount of water required for the hydrolysis and condensation is then metered in at room temperature. The reaction mixture is then preferably stirred at room temperature for 12 to 36 hours. The amount of water is metered in so that local over-concentrations are avoided. This can be regulated via the feed rate or it can be achieved, for example, by adding the amount of water to the reaction mixture with the aid of moisture-laden adsorbents, e.g. silica gel or molecular sieves, water-containing organic solvents, e.g. 80% ethanol, or salt hydrates, e.g. CaC x 6H ₂ 0.

The hydrolysis and condensation are preferably carried out in the presence of a hydrolysis and condensation catalyst.

Proton- or hydroxyl-ion-releasing compounds and amines are suitable as hydrolysis and condensation catalysts. Specific examples are organic or inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, and organic or inorganic bases such as ammonia, alkali or alkaline earth metal hydroxides, for example sodium, potassium or calcium hydroxide, and amines soluble in the reaction medium, for example lower alkylamines or alkanolamines , Here are volatile acids and bases, in particular Hydrochloric acid, acetic acid, ammonia or triethylamine are particularly preferred.

The resulting sols according to the invention can also contain customary and known additives (H). Suitable are all additives (H) which do not adversely affect the profile of properties of the coatings, adhesive layers and seals, in particular the optical properties (appearance) and scratch resistance of the coatings, but which vary and improve in an advantageous manner.

If the sols according to the invention are to be used for the production of color and / or effect coatings, they contain at least one pigment as additive (H).

The pigments (H) are preferably selected from the group consisting of customary and known organic and inorganic color and / or effect-giving, electrically conductive, magnetically shielding and fluorescent pigments and customary and known organic and inorganic fillers.

Furthermore, the sols according to the invention can contain additives (H) which can be used both in the pigmented and in the unpigmented sols according to the invention. Examples of suitable additives (H) are from German patent applications DE 199 24 170 A1, column 13, page 6, to column 14, line 2, DE 199 24 171 A1, page 8, line 65, to page 9, line 33 , or DE 198 39 453 A1, page 6, line 68, to page 7, page 6.

Last but not least, the brine according to the invention can contain photoinitiators as additives (H). Suitable photoinitiators (H) are those of

Norrish Il-type, whose mechanism of action is based on an intramolecular Variant of the hydrogen abstraction reactions is based on how they occur in many different ways in photochemical reactions (for example, reference is made here to Römpp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991), or cationic photoinitiators ( For example, reference may be made here to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446), in particular benzophenones, benzoins or benzoin ethers or phosphine oxides. The products commercially available under the names Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Rahn and Lucirin® TPO from BASF AG can also be used, for example.

The additives (H) can be added before, during and / or after the preparation of the brine according to the invention; they are preferably added after production.

The solids content of the brine according to the invention can vary very widely and depends on the particular intended use. If the sols according to the invention are used, for example, as unpigmented coating materials for the production of thin, highly scratch-resistant coatings with a layer thickness of <5 μm, the solids content is preferably below 50, preferably below 40, particularly preferably below 30 and in particular below 20% by weight, based on the respective sol according to the invention. If the sols according to the invention are to be used, for example, as constituents of dual-cure coating materials, the solids content is preferably 10 to 90, preferably 15 to 85, particularly preferably 20 to 80, very particularly preferably 25 to 75 and in particular 30 to 70% by weight. %, based on the respective sol according to the invention. The person skilled in the art can determine advantageous solids contents of brines according to the invention which are to be used for other purposes on the basis of his general knowledge If necessary, adjust your specialist knowledge with the help of simple preliminary tests.

The production of the brine according to the invention has no special features in terms of method, but instead takes place by mixing the components described above. Mixing units such as stirred kettles, dissolvers, in-line dissolvers, agitator mills, static mixers, gear rim dispersers or extruders can be used. This is preferably carried out with the exclusion of actinic radiation in order to avoid damage to the brine according to the invention, in particular by premature crosslinking.

The sols according to the invention can be used as such as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals. They are preferably used as coating materials for the production of pigmented and unpigmented, in particular non-pigmented, coatings. The brine according to the invention provide thin, highly scratch-resistant coatings that adhere firmly to a wide variety of substrates.

The brines according to the invention are particularly preferably used as a constituent of dual-cure coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals. The sols according to the invention are very particularly preferably used as a constituent of dual-cure coating materials, in particular dual-cure clearcoats.

Dual-cure coating materials, in particular dual-cure clearcoats, the thermally and / or components curable with actinic radiation, such as

Binder, crosslinking agent and optionally reactive diluent are contained, for example, from German patent applications DE 198 18 735 A1, DE 199 08 013 A1, DE 199 08 018 A1, DE 199 20 799 A1 or DE 199 20 801 A1, European patent application EP 0 928 800 A 1 or the international patent application WO 98/40170 are known or they are described in the unpublished German patent application DE 100 41 635.7.

These dual-cure coating materials can be one-component systems in which the crosslinking agents and the binders are present side by side. They can also be multicomponent systems in which, owing to the high reactivity of the crosslinking agents, such as, for example, those from German patent application DE 199 24 171 A1, page 7, line 38, to page 8, line 46, in conjunction with Page 3, line 43, to page 5, line 31, partially blocked or unblocked polyisocyanates, binders and crosslinking agents must be stored separately from one another until shortly before application. The dual-cure clearcoats are preferably one-component systems.

A particularly advantageous dual-cure coating material contains

(I) at least one crosslinking agent containing, on average, at least one blocked isocyanate group and at least one reactive functional group with at least one bond which can be activated with actinic radiation, and

(II) at least one binder with a statistical average of at least one isocyanate-reactive functional group.

Here come as blocking agents, as reactive functional groups with at least one bond that can be activated with actinic radiation the groups described above are considered as isocyanate-reactive functional groups.

The crosslinking agent (I) can be prepared in any manner.

However, crosslinking agents (I) which are prepared from at least one polyisocyanate with an isocyanate functionality of at least 2.0 are particularly advantageous. The polyisocyanate preferably had an isocyanate functionality of 2.0 to 6.0, preferably 2.0 to 5.0, particularly preferably 2.0 to 4.5 and in particular 2.0 to 3.5. In view of the better weather resistance and yellowing resistance, aliphatic and cycloaliphatic polyisocyanates are preferably used. In the context of the present invention, the term “cycloaliphatic diisocyanate” denotes a diisocyanate in which at least one isocyanate group is bonded to a cycloaliphatic radical.

Examples of suitable cycloaliphatic polyisocyanates with an isocyanate functionality of 2.0 are isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1, 3,3-trimethyl-cyclohexane), 5-isocyanato-1 - (2-isocyanatoeth-1-yl) - 1,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) - 1, 3,3-trimethylcyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2 - (4-isocyanatobut-1-yl) cyclohexane, 1, 2-diisocyanatocyclobutane, 1, 3-diisocyanatocyclobutane, 1, 2-

Diisocyanatocyclopentane, 1, 3-diisocyanatocyclopentane, 1, 2-

Diisocyanatocyclohexane, 1, 3-diisocyanatocyclohexane, 1, 4-

Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate or dicyclohexylmethane-4,4'-diisocyanate, especially isophorone diisocyanate. Examples of suitable acyclic aliphatic diisocyanates with an isocyanate functionality of 2.0 are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate,

Hexamethylene diisocyanate, ethylethylene diisocyanate, trimethylhexane diisocyanate, heptamethylene diisocyanate or diisocyanates, derived from dimer fatty acids, as sold by Henkel under the trade name DDI 1410 and described in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3 , 4-bis (9-isocyanatononyl) -1-pentylcyclohexane, or 1, 2-, 1, 4- or 1, 3- bis (isocyanatomethyl) cyclohexane, 1, 2-, 1, 4- or 1, 3rd Bis (2-isocyanatoeth-1-yl) cyclohexane, 1, 3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1, 2-, 1, 4- or 1, 3-bis (4-isocyanatobut-1 -yl) cyclohexane, in particular

Hexamethylene diisocyanate.

Examples of suitable polyisocyanates with an isocyanate functionality> 2 are polyisocyanates, in particular based on hexamethylene diisocyanate, which contain isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups and which are more commonly known Ways are obtainable from the diisocyanates described above. Of these, the allophanate groups are advantageous and are therefore used with particular preference in accordance with the invention. Examples of suitable production processes and polyisocyanates are from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A 1, US 4,801, 675 A, EP 0 183 976 A 1, DE 40 15 155 A 1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A, US 5,290,902 A, EP 0 649 806 A 1, DE 42 29 183 A1 or EP 0 531 820 A 1 known.

The polyisocyanates described above are mixed with at least one compound which has at least one, in particular one, isocyanate-reactive functional group and contains at least one, in particular one, bond that can be activated with actinic radiation. Examples of suitable compounds having at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, bond which can be activated with actinic radiation are per molecule

Allyl alcohol or 4-butyl vinyl ether;

- Hydroxyalkyl esters and hydroxycycloalkyl esters of acrylic acid or methacrylic acid, in particular acrylic acid, which can be obtained by esterifying aliphatic diols with acrylic acid or methacrylic acid or by reacting acrylic acid or methacrylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid or methacrylic acid, in which the

Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane acrylate or methacrylate; Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly advantageous and are therefore used with particular preference in accordance with the invention; or

Reaction products from cyclic esters, such as e.g. epsilon-caprolactone, and this hydroxyalkyl or cycloalkyl ester.

In addition, the polyisocyanates are reacted with at least one of the blocking agents described above.

In a first preferred variant, the crosslinking agent (I) is prepared by reacting the compounds described above with the polyisocyanates in one Molar ratio that on statistical average at least one free isocyanate group remains in the resulting adduct, which is available for the reaction with the blocking agents described above.

In a second preferred variant, the crosslinking agent (I) is prepared by reacting the blocking agents described above with the polyisocyanates in a molar ratio such that, on statistical average, at least one free isocyanate group remains in the adduct for reaction with the compounds described above Available.

In a third preferred variant, the crosslinking agent (I) is prepared by reacting the compounds described above and the blocking agents described above in a one-pot process with the polyisocyanates.

Irrespective of which variant is chosen for the preparation of the crosslinking agent (I), there are no longer any free isocyanate groups present or no longer detectable.

The content of the crosslinking agents (I) in the one-component system according to the invention can vary very widely and depends in particular on the functionality of the other essential constituents with regard to the crosslinking reactions and on the crosslinking density which is to be set in the coatings, adhesive layers or seals. The content of crosslinking agents (I) is preferably 10 to 60, preferably 15 to 55, particularly preferably 20 to 50 and in particular 25 to 45% by weight, in each case based on the solids of the one-component system according to the invention. The further essential component of the one-component system according to the invention is at least one binder (II) with an average of at least one, in particular at least two, isocyanate-reactive functional groups in the molecule. Examples of suitable isocyanate-reactive functional groups are those described above. The binder (II) can additionally contain at least one, in particular at least two, of the functional groups described above with at least one bond which can be activated with actinic radiation.

Examples of suitable binders (II) are random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyadditionharze (polyadducts)", as well as pages 463 and 464, "Polycondensates", "Polycondensation" and

"Polycondensation resins", as well as pages 73 and 74, "Binder".

Examples of suitable (co) polymers (II) are

(Meth) acrylate (co) polymers or partially saponified polyvinyl esters, especially (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or

Polycondensation resins (II) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester-polyurethanes. Of these binders (II), the (meth) acrylate copolymers have particular advantages and are therefore used with particular preference.

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

(1) Monomers which carry at least one hydroxyl or amino group per molecule, such as

Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha.beta-olefinically unsaturated carboxylic acid which are derived from an alkylene glycol which is esterified with the acid, or which can be obtained by reacting the alpha.beta- olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the

Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1, 4-

Bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1 H-indene-dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofumarate or monoitaconate; Reaction products from cyclic esters, such as epsilon-caprolactone and these hydroxyalkyl or cycloalkyl esters;

olefinically unsaturated alcohols such as allyl alcohol;

Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;

Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, or instead of the reaction product, an equivalent amount of acrylic and / or methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;

- aminoethyl acrylate, aminoethyl methacrylate, allylamine or N -

Methyliminoethylacrylat; and or

Acryloxysilane-containing vinyl monomers, which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with

(Meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid and / or other hydroxyl group-containing monomers (b1).

(2) monomers which carry at least one acid group per molecule, such as Acrylic acid, beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;

olefinically unsaturated sulfonic or phosphonic acids or their partial esters;

Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or

Phthalate (meth) acryloyloxyethyl ester; or

Vinylbenzoic acid (all isomers), alpha

Methyl vinyl benzoic acid (all isomers) or vinyl benzene sulfonic acid (all isomers).

(3) Monomers that are substantially or completely free of reactive functional groups, such as:

Monomers (31):

Essentially acid group-free (meth) acrylic esters such as (meth) alkyl or cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl , Hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic

(Meth) acrylic acid esters, especially cyclohexyl, isobomyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene-methanol- or tert-butylcyclohexyl (meth) acrylate;

(Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethoxytriglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with a molecular weight Mn of preferably 550 or others Ethoxylated and / or propoxylated hydroxyl group-free (meth) acrylic acid derivatives (further examples of suitable monomers (b31) of this type are known from published patent application DE 196 25 773 A1, column 3, line 65, to column 4, line 20). These can be more functional in minor quantities

(Meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, octahydro-4,7-methano- 1 H-indene-dimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or

Contain pentaerythritol di-, tri- or tetra (meth) acrylate. In the context of the present invention, minor amounts of higher-functional monomers (b31) are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, unless they should be in the form of crosslinked microgel particles.

Monomers (32):

Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule, branched in the alpha position. The branched

Monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom. Other olefinic

Starting materials are propylene trimer, propylene tetramer and Diisobutylene. However, the vinyl esters can also be prepared from the acids in a manner known per se, for example by letting the acid react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).

Monomers (33):

Diarylethylenes, especially those of the general formula VI:

wherein the radicals R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl ₇ or arylcycloalkyl radicals with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 represent} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are

Cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl,

Naphthyl or biphenylyl, preferably phenyl and naphthyl and especially phenyl. Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylphen-1-yl. Examples of more suitable

Arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl. The aryl radicals R ¹ , R ² , R ³ and / or R ⁴ are preferably phenyl or naphthyl radicals, in particular phenyl radicals. The substituents optionally present in the radicals R ¹ , R ² , R ³ and / or R ⁴ are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and

cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals. Diphenylethylene, dinaphthaleneethylene, eis or trans-stilbene or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous, which is why they are preferably used. As part of the present

According to the invention, the monomers (b33) are used in order to regulate the copolymerization in an advantageous manner in such a way that free-radical copolymerization in a batch mode is also possible.

Monomers (34):

Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.

Monomers (35):

Nitriles such as acrylonitrile and / or methacrylonitrile. Monomers (36):

Vinyl compounds, especially vinyl and / or

Vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinyl amides such as vinyl

N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.

Monomers (37):

Allyl compounds, especially allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.

Monomers (38):

Polysiloxane macromonomers, which are number average

Molecular weight Mn from 1,000 to 40,000 and on average 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; especially polysiloxane macromonomers, which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferred

2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as described in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A 1 in columns 3 to 7, EP 0 358 153 B 1 on pages 3 to 6, in the

No. 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line 10.

Monomers (39):

Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.

and or

(4) Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, ^~ methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid or allyl glycidyl ether.

Higher functional monomers of the type described above are generally used in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are understood to mean amounts which are not suitable for crosslinking or gelling the (meth) acrylate copolymers (II). unless you want to specifically manufacture cross-linked polymeric microparticles.

Examples of suitable production processes for (meth) acrylate copolymers (II) are described in European patent applications EP 0 767 185 A 1, German patents DE 22 14 650 B1 or DE 27 49 576 B1 and American patents US 4,091,048 A1 , US 3,781, 379 A 1, US 5,480,493 A 1, US 5,475,073 A 1 or US 5,534,598 A 1 or in the standard work Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255 , 1961. Suitable reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tubular reactors, visual reactors or Taylor reactors, as described, for example, in the patents and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A. 1 or in the article by K. Kataoka in Chemical Engineering Science, Volume 50, Issue 9, 1995, pages 1409 to 1416.

Functional groups with at least one bond which can be activated by actinic radiation can be introduced by polymer-analogous reaction of the (meth) acrylate copolymers (II) described above with suitable compounds which contain bonds which can be activated by actinic radiation. For example, any side glycidyl groups of the (meth) acrylate copolymers (II) which are present can be reacted with (meth) acrylic acid.

The content of binders (II) in the one-component system according to the invention can likewise vary very widely and depends in particular on the functionality of the binders (II) with regard to the crosslinking reactions. The content is preferably 5 to 40, preferably 6 to 35, particularly preferably 7 to 30 and in particular 8 to 25% by weight, based in each case on the solid of the one-component system according to the invention.

The third essential component of the one-component system according to the invention is the sol according to the invention described above. The content of the sol according to the invention in the one-component system according to the invention can likewise vary widely. The sol solids content is preferably 5 to 70, preferably 6 to 65, particularly preferably 7 to 60 and in particular 8 to 55% by weight, in each case based on the solids of the one-component system according to the invention.

In addition, the one-component system according to the invention can also contain at least one of the compounds (B) described above, which is not introduced via the brine according to the invention. The amount of additional compounds (B) is preferably 5 to 40, preferably 6 to 35, particularly preferably 7 to 30 and in particular 8 to 25% by weight, in each case based on the solids of the one-component system according to the invention.

In addition, the one-component system according to the invention can likewise contain at least one of the additives (H) described above. The selection depends primarily on the intended use of the one-component system according to the invention.

The one-component system according to the invention can serve as a dual-cure adhesive, dual-cure sealant or dual-cure coating material.

The dual-cure adhesives, sealants and coating materials can be used in liquid solvent-containing systems (conventional Systems), liquid solvent-free systems (100% systems) or solvent-free solid systems. In the case of coating materials, the solvent-free solid systems are also referred to as powder coatings. These can also be dispersed in water. Experts also refer to dispersions of this type as powder slurry coatings. Liquid, solvent-based, ie conventional, dual-cure adhesives, sealing compounds and coating materials are preferably used.

The one-component system according to the invention is particularly preferably used as a dual-cure clearcoat, in particular as a conventional dual-cure clearcoat. In this case, the solids content is preferably 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight, in each case based on the one-component system according to the invention.

The production of the one-component systems according to the invention has no special features in terms of method, but the methods and devices described above for the brines according to the invention can be used.

The dual-cure adhesives according to the invention serve to produce the adhesive layers according to the invention on primed and unprimed substrates.

The dual-cure sealing compounds according to the invention are used to manufacture the seals according to the invention on and / or in primed and unprimed substrates. The dual-cure coating materials are used to produce single- or multi-layer clearcoats and / or color and / or effect coatings on primed and unprimed substrates.

The one-component systems according to the invention prove to be particularly advantageous precisely for this use. Very particular advantages result when they are used for the production of clearcoats, in particular in the context of the so-called wet-on-wet process, in which a basecoat, in particular a waterborne basecoat, is applied to the primed or unprimed substrate and dried, but is not cured, after which a clear coat is applied to the base coat layer and the resulting clear coat layer is cured together with the base coat layer thermally and with actinic radiation.

Suitable substrates are all surfaces to be painted, glued and / or sealed which are not damaged by the hardening of the layers thereon under the combined use of heat and actinic radiation.

Suitable substrates consist of metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials.

Accordingly, the dual-cure coating materials, adhesives and sealants according to the invention for the coating, bonding and sealing of motor vehicle bodies or parts thereof, of motor vehicles indoors and outdoors, of buildings indoors and outdoors, of furniture, windows and doors as well as in the context of industrial painting for the coating, gluing and sealing of small parts such as nuts, screws, hubcaps or rims Coils, containers, packaging, electrical components, such as motor windings or transformer windings, and white goods, such as household appliances, boilers and radiators, are excellently suited.

In the case of electrically conductive substrates, primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.

Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, GAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted, glued or sealed. In the case of non-functionalized and / or non-polar substrate surfaces, these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.

The dual-cure coating materials, adhesives and sealants, in particular the dual-cure coating materials, can be applied by all customary application methods, such as spraying, spraying, brushing, pouring, dipping, soaking, trickling or rolling. The substrate to be coated can rest as such, with the application device or system being moved. However, the substrate to be coated, in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner. Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application, such as hot air hot spraying. The applications can be used at temperatures of max. 70 to 80.degree. C. are carried out so that suitable application viscosities are achieved without the change in or damage to the coating material and its overspray, which may have to be reprocessed, occurring during the briefly acting thermal load. For example, hot spraying can be designed in such a way that the dual-cure coating material is heated only very briefly in or shortly before the spray nozzle.

The spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the coating material itself is operated.

The application is preferably carried out when illuminated with visible light of a wavelength of over 550 nm or with exclusion of light. This avoids material changes or damage to the dual-cure coating material and the overspray.

In general, the one-component systems according to the invention for the production of filler coatings, solid-color top coats, base coats and clear coats are applied in a wet layer thickness so that after curing, layers with the necessary and advantageous layer thicknesses for their functions result. In the case of filler coatings, this layer thickness is 10 to 150, preferably 15 to 120, particularly preferably 20 to 100 and in particular 25 to 90 μm, in the case of solid-color coating it is 5 to 90, preferably 10 to 80, particularly preferably 15 to 60 and in particular 20 to 50 μm, in In the case of the basecoat, it is 5 to 50, preferably 6 to 40, particularly preferably 7 to 30 and in particular 8 to 25 μm, and in the case of the clearcoats it is 10 to 100, preferably 15 to 90, particularly preferably 20 to 85 and in particular 25 to 80 μm.

The hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 30 min. The rest period is used, for example, for the course and degassing of the applied layers or for the evaporation of volatile components such as solvents or water. The rest period can be supported and / or shortened by using elevated temperatures up to 80 ° C, provided that there is no damage or changes to the applied layers, such as premature complete crosslinking.

According to the invention, curing takes place with actinic radiation, in particular with UV radiation, and / or electron beams. If necessary, it can be carried out or supplemented with actinic radiation from other radiation sources. In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the applied layers.

In the case of curing with UV radiation, it is also possible to work under inert gas in order to avoid the formation of ozone. It is preferred to work in an oxygen-depleted atmosphere.

The usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.

Examples of suitable radiation sources are high or - mercury low-pressure vapor lamps, which may be doped with lead to open a radiation window up to 405 nm, or electron beam sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.

In the case of workpieces of complicated shape such as automobile bodies, the areas (shadow areas) which are not accessible to direct radiation, such as cavities, folds and other design-related areas, can be used

Undercuts with point, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or edges, are cured.

The facilities and conditions of these hardening methods are described, for example, in R. Holmes, UN. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984. Further examples of suitable methods and devices for curing with actinic radiation are described in German patent application DE 198 18 735 A1, column 10, lines 31 to 61.

The curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.

The thermal curing also has no special features in terms of method, but is carried out according to the customary and known methods, such as heating in a forced air oven or irradiation with IR lamps. As with curing with actinic radiation, thermal curing can also be carried out in stages. The thermal curing advantageously takes place at a temperature> 90 ° C., preferably 90 to 180 ° C., particularly preferably 110 to 160 ° C and in particular 120 to 150 ° C for a period of 1 min to 2 h, particularly preferably 2 min to 1 h and in particular 3 min to 30 min.

Thermal curing and curing with actinic radiation can be used simultaneously or alternately. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start and end the curing with actinic radiation. The person skilled in the art can determine the hardening method which is most advantageous for the individual case on the basis of his general specialist knowledge, if necessary with the aid of simple preliminary tests.

Another advantage of the new dual-cure coating materials, adhesives and sealants is that they can also be used in the shadow areas of complex three-dimensional substrates, such as car bodies, radiators or electrical winding goods, even without optimal, in particular complete, illumination of the shadow areas with actinic radiation Deliver coatings, adhesive layers and seals whose application properties profile at least matches that of the coatings, adhesive layers and seals outside the shadow zones. As a result, the coatings, adhesive layers and seals located in the shadow zones are also no longer easily damaged by mechanical and / or chemical action, such as can occur when other components of motor vehicles are installed in the coated bodies.

The adhesive layers according to the invention produced from the dual-cure adhesives and sealing compounds according to the invention Seals have excellent adhesive strength and sealability even over long periods of time, even under extreme and / or rapidly changing climatic conditions.

The coatings according to the invention produced from the dual-cure coating materials according to the invention have an excellent flow and an excellent overall optical impression. They are weather-resistant and do not yellow even in tropical climates. They can therefore be used indoors and outdoors.

The color and / or effect multi-layer coatings produced with the help of the dual-cure coating materials are what color, effect, gloss and D.O.I. (distinctiveness of the reflected image), of the highest optical quality, have a smooth, structure-free, hard, flexible and scratch-resistant surface, are weather, chemical and etch resistant, they do not yellow and show no cracking and delamination of the layers.

Therefore, the primed and unprimed substrates according to the invention, in particular bodies of automobiles and commercial vehicles, industrial components, including plastic parts, small parts, packaging, coils, white goods and electrical components, or furniture, doors or windows coated with at least one coating according to the invention, sealed with at least one seal according to the invention and / or glued with at least one adhesive according to the invention, special technical and economic advantages, in particular a long service life, on what makes them particularly attractive for users.

Examples Production Example 1

The preparation of a binder (II)

In a laboratory reactor with a usable volume of 4 l, which was equipped with a stirrer, a dropping funnel for the monomer feed and a dropping funnel for the initiator feed, nitrogen inlet tube, thermometer and reflux condenser, 650 parts by weight of a fraction of aromatic hydrocarbons with a boiling range of 158 to 172 ° C submitted. The solvent was heated to 140 ° C, at which temperature a monomer mixture of 652 parts by weight of ethyl hexyl acrylate, 383 parts by weight of hydroxyethyl methacrylate, 143 parts by weight of styrene, 213 parts by weight of 4-hydroxybutyl acrylate and 49 parts by weight of acrylic acid was stirred for four hours and an initiator solution of 113 parts by weight at this temperature - Butyl perethylhexanoate and 113 parts by weight of the aromatic solvent were metered in uniformly over the course of four and a half hours. The inlets were started at the same time. After the end of the initiator feed, the editorial mixture was kept at 140 ° C. for two hours and then cooled. The reaction mixture was diluted with a mixture of 1-methoxypropylacetate-2, butylglycol acetate and butyl acetate. The resulting binder solution (II) had a solids content of 65% by weight (1 h / 130 ° C.).

Preparation example 2

The preparation of a crosslinking agent (I)

1,538 parts by weight of a commercially available acrylate- and isocyanate-functional polyisocyanate (Roskydal® UA VPLS 2337 der Bayer AG) were dissolved in 838 parts by weight of a fraction of aromatic hydrocarbons with a boiling range of 158 to 172 ° C. The solution was weighed into a reactor equipped with a stirrer, reflux condenser and oil heating and heated to 60.degree. 418 parts by weight of dimethylpyrazole were added in three portions via a solids metering device, an exothermic reaction occurring with each addition. After each of the additions, the exothermic reaction had to be waited for before the next addition took place. The content of free isocyanate groups was determined every hour. If the isocyanate content was <0.01%, the solution was cooled to room temperature and filtered. The solution (I) had a solids content of 70% by weight.

Examples 1 and 2

The production of brine 1 and 2 according to the invention

Aluminum tri-sec-butoxide and dimethyldlethoxysilane and an equimolar amount of acetoacetic acid ester (based on the aluminate) were added in a suitable stirred vessel with stirring so that the temperature remained below 30 ° C. Dipentaerythritol pentaacrylate and the other hydrolyzable silicon compounds were then added with stirring. The resulting mixture was homogenized for 30 minutes. At room temperature, water was metered into the mixture at a rate of about 0.4 ml / min with stirring over a period of 45 minutes. The resulting reaction mixture was stirred at room temperature for 24 hours.

The starting products and their quantities can be found in Table 1. Table 1: The starting products for the brine 1 and 2 according to the invention their amounts

Starting product Examples: 1 2

Mol% by weight mol% by weight

Aluminum tri-sec-butylate 0.2 12.4 0.2 11.7

Dimethyldiethoxysilane 0.13 4.7 0.12 4.4

3-aminopropyltriethoxysilane 0.05 2.8 0.05 2.6

3-methacryloxypropyltrimethoxysilane 0.3 18.7 0.3 17.7

3-Isocyanatopropyltriethoxysilane blocked with dimethylpyrazole 0.15 13.6 0.3 25.7

Glycidoxypropyltrimethoxysilane 0.15 8.9

Acetoacetic acid ester 0.2 6.5 0.2 6.2

Water 2.6 11, 7 2.6 11, 1 Dipentaerythritpenta-

Acrylate - 20.7 - 20.7

Solids content (15 minutes / 180 ° C) (% by weight) - 57.2 - 57.2

The sols of Examples 1 and 2 according to the invention were outstandingly suitable for the production of thin, highly scratch-resistant coatings for a wide variety of substrates. They were also extremely suitable for the production of dual-cure clearcoats according to the invention. Despite being produced at room temperature, they were extremely stable in storage without having to be cooled. This was particularly advantageous in terms of logistics, equipment, process technology and security. ^>

Examples 3 and 4

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

For the preparation of the dual-cure clearcoats of Examples 3 and 4 according to the invention, a base coat of 35.9 parts by weight of the binder solution (II) from Preparation 1, 1.0 parts by weight of a substituted hydroxyphenyltriazine (65% in toluene), 1 , 0 parts by weight of N-aminoether-2,2,6,6-tetramethyl-piperidinyl ester (Tinuvin® 123 from Ciba Specialty Chemicals), 0.4 parts by weight of a leveling agent (BYK® 306 from Byk Chemie), 0.5 part by weight of lucirin ® TPO (photoinitiator from BASF Aktiengesellschaft), 1.0 part by weight Genocure® MBF (photoinitiator from Rahn), 2.0 parts by weight of Irgacure® 184 (photoinitiator from Specialty Chemicals, Inc.), 10.8 parts by weight of solvent naphtha and 27.4 parts by weight of butyl diglycol acetate.

The base lacquer, the crosslinking agent (I) according to preparation example 2 and the sols 1 and 2 according to the invention according to examples 1 and 2 and a solution containing dibutyltin dilaurate (crosslinking catalyst) were mixed together in the quantitative ratios shown in table 2 and homogenized.

Table 2: The material composition (in% by weight) of the dual-cure clearcoats of Examples 3 and 4

Part examples:

1 2

Master varnish 34.82 34.82

Sol according to Example 1 41, 98

Sol according to Examples 2 - 41, 98

Crosslinking agent II according to

Preparation Example 2 22.76 22.76

Dibutyltin dilaurate solution 0.44 0.44 The dual-cure clearcoats of Examples 3 and 4 were each adjusted with 27.4 parts by weight of butyl acetate and 10 parts by weight of solvent naphtha to a viscosity of 18 seconds in a A4 flow cup and sieved (mesh size 31 μm). They were used for the production of clear coats in multi-layer paint systems.

To produce the multi-layer coatings, test panels made of steel, which were coated with electro-dip coatings with a dry film thickness of 18 to 22 μm, were coated with a water filler. The resulting water filler layers were baked at 165 ° C. for 20 minutes, so that filler coatings with a dry layer thickness of 35 to 40 μm resulted. The filler coatings were then coated with a black water-based lacquer in a layer thickness of 12 to 15 μm, and the resulting water-based lacquer layers were flashed off at 80 ° C. for 10 minutes. The clearcoats of Examples 3 and 4 were then applied wet-on-wet pneumatically in a cloister with a gravity-cup gun. The clear lacquer layers were flashed off at room temperature for 5 minutes.

Subsequently, in a first series, the water-based lacquer layers and the clear lacquer layers were thermally cured in a forced-air oven for 20 minutes at 140 ° C. The thermally cured clear lacquer layers were then cured with UV radiation (dose: 1,500 mJ / cm ² ). The result was clear coats with a dry film thickness of 60 to 65 μm.

In order to simulate the hardening of the clear lacquer layers in the shadow zones, the clear lacquer layers were only thermally hardened in a second series, the conditions described above being applied. The multilayer coatings of the first series according to the invention were tested as follows:

The gloss and haze of the multi-layer coatings were determined in accordance with DIN 67530.

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

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

The scratch resistance was also determined after the brush test. For this test, the test panels with the multi-layer coatings were stored at room temperature for at least 2 weeks before the test was carried out. The procedure described in FIG. 2 on page 28 of the article by P. Betz and A. Bartelt, Progress in Organic Coatings, 22 (1993), pages 27-37, was applied, although it was based on the weight used (2000 g instead of the 280 g mentioned there was modified. In the test, the paint surface was covered with a Sieve fabric, which was loaded with a mass, damaged. The screen fabric and the varnish surface were wetted liberally with a detergent solution. The test panel was moved back and forth under the screen fabric in a lifting motion by means of a motor drive. The test specimen was eraser covered with nylon sieve mesh (No. 11, 31 μm mesh size, Tg 50 ° C.) (4.5 × 2.0 cm, wide side perpendicular to the direction of scratching). The coating weight was 2000 g. Before each test, the screen mesh was renewed, the running direction of the mesh was parallel to the scratch direction. With a pipette, approx. 1 ml of a freshly stirred 0.25% Persil solution was applied in front of the eraser. The number of revolutions of the motor was set so that 80 double strokes were carried out in a time of 80 s. After the test, the remaining washing liquid was rinsed with cold tap water and the test panel was blown dry with compressed air. The gloss was measured according to DIN 67530 before and after damage (measuring direction perpendicular to the scratch direction).

In addition, the scratch resistance was determined according to the Amtec-Kistler test known in the art (cf. T. Klimmasch, T. Engbert, Technologietage, Cologne, DFO, Report Volume 32, pages 59 to 66, 1997).

The scratch resistance was also determined using the steel wool test. For this purpose, the flat side of a locksmith hammer according to DIN 1041 was covered with a layer of steel wool. Then the hammer was carefully placed on the clearcoats at a right angle and passed over the clearcoats in a trace without tilting and without additional physical strength. In each test, 10 double strokes had to be carried out over 15 seconds. The damage pattern was graded as follows: Note damage pattern

1 no scratches

2 small number of scratches 3 moderate number of scratches

4 medium number of scratches

5 large number of scratches

6 a lot of scratches

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

The multi-layer coatings of the second series were subjected to the fingernail test.

The application technology properties determined in this way are summarized in Table 3.

Table 3: Important application properties of the multi-layer coatings of Examples 3 and 4

Property examples: 3

Shine (units): 91 91 Haze (units): 12 17

Micro penetration hardness (mN): 131, 1 133.1

Scratch resistance after the brush test Gloss difference (units): 3.8

Scratch resistance after the sand test Gloss difference (units): 11, 5 9.1

Amtec-Kistler scratch resistance: gloss difference before cleaning (units): 32 23

Gloss difference after cleaning with ethanol (units): 24 20

Scratch resistance to steel wool:

(10 double strokes) (grade): 3 5

(200 double strokes) (grade): 3 5

Depth of scratches after

200 double strokes: superficial superficial

Shadowed areas cure: Fingernail test: tough-flexible tough-flexible not scratchable not scratchable

The results summarized in Table 3 show that the multi-layer coatings according to the invention had a high gloss, a low haze, very good hardness and a particularly high scratch resistance even in the shadow zones.

Claims

Polysiloxane brines curable thermally and with actinic radiation, process for their preparation and their use

1.Thermally and with actinic radiation curable polysiloxane brine (dual-cure polysiloxane brine) can be produced by hydrolysis and condensation

(A) at least one hydrolyzable silicon compound of the general formula I:

X _m Si (RY _n ) ₄ . _m (I),

where the indices and the variables have the following meaning:

m 1, 2 or 3;

n 1, 2 or 3;

X hydrolyzable residue;

R non-hydrolyzable divalent organic residue;

Y blocked isocyanate group;

in the presence of

(B) at least one compound containing at least one reactive functional group with at least one actinic radiation activatable bond and at least one isocyanate-reactive functional group.

2. Dual-cure polysiloxane brine according to claim 1, characterized in that it by hydrolysis and condensation in the

presence

(C) at least one hydrolyzable silicon compound of general formula II:

X _m Si (RZ _n ) ₄ - _m (II),

where the indices and the variables have the following meaning:

m 1, 2 or 3;

n 1, 2 or 3;

X hydrolyzable residue;

R non-hydrolyzable divalent organic residue;

Z isocyanate-reactive functional group, reactive functional group with at least one bond that can be activated with actinic radiation and / or epoxy group;

are producible.

3. Dual-cure polysiloxane brine according to claim 1 or 2, characterized in that it is present

(D) at least one hydrolyzable silicon compound of the general formula III:

XpSiRVp (III),

where the indices and the variables have the following meaning:

p 1, 2, 3 or 4;

X hydrolyzable residue;

R ^' non-hydrolyzable monovalent organic residue;

are producible.

4. Dual-cure polysiloxane brine according to one of claims 1 to 3, characterized in that it is present

(E) at least one hydrolyzable metal compound of the general formula IV:

XpMR ^' _r . _P (IV),

where the indices and the variables have the following meaning:

p and r is an integer between 1 and 4, with the proviso that p + r = 2, 3 or 4;

M tin, boron, aluminum, titanium or zirconium;

X hydrolyzable residue;

R ^' non-hydrolyzable monovalent organic residue;

are producible.

5. Dual-cure polysiloxane brine according to one of claims 1 to 4, characterized in that it is present

(F) at least one organic thio compound of the general formula V:

S (RZ _n ) ₂ (V),

where the index and the variable are those given above

Have meaning;

are producible.

6. Dual-cure polysiloxane brine according to one of claims 1 to 5, characterized in that they can be prepared by hydrolysis, condensation and complexation.

7. Dual-cure polysiloxane brine according to claim 6, characterized in that the complexing agent (G) from the group of the organic compounds that form chelating ligands.

8. Dual-cure polysiloxane brine according to one of claims 1 to 7, characterized in that the isocyanate-reactive functional

Groups from the group consisting of thiol groups,

Hydroxyl groups and primary and secondary amino groups can be selected.

9. Dual-cure polysiloxane brine according to one of claims 1 to 8, characterized in that the bonds which can be activated with actinic radiation are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon- Phosphorus or carbon-silicon single bonds or double bonds are.

10. Dual-cure polysiloxane brine according to claim 9, characterized in that the bonds which can be activated with actinic radiation are carbon-carbon double bonds ("double bonds").

11. Dual-cure polysiloxane sols according to claim 10, characterized in that the groups containing double bonds from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl .

Norbornenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups can be selected.

12. Dual-cure polysiloxane brine according to one of claims 1 to 11, characterized in that the indices m and n independently of one another represent 1.

13. Dual-cure polysiloxane brine according to one of claims 1 to 12, characterized in that the hydrolyzable radicals X from the group consisting of hydrogen atoms and halogen atoms, hydroxyl groups and primary and secondary amino groups as well as substituted and unsubstituted alkoxy, cycloalkoxy , Aryloxy, acyloxy, alkoxycarbonyl, cycloalkoxycarbonyl and

Aryloxycarbonyl groups.

14. Dual-cure polysiloxane brine according to claim 13, characterized in that the hydrolyzable radicals X are selected from the group of alkoxy groups having 1 to 4 carbon atoms in the alkylene radical.

15. Dual-cure polysiloxane brine according to one of claims 1 to 14, characterized in that the non-hydrolyzable, double-bonded organic radicals from the group consisting of double-bonded radicals which are derived from at least one of the following organic compounds:

(i) Substituted and unsubstituted, linear or branched alkanes, alkenes, cycloalkanes containing no or at least one hetero atom in the chain and / or in the ring,

Cycloalkenes, alkylcycloalkanes, alkylcycloalkenes,

Alkenylcycloalkanes or alkenylcycloalkenes;

(ii) substituted and unsubstituted aromatics or

heteroaromatics; such as (iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or

Alkenylcycloalkenyl-substituted aromatics or

Heteroaromatics, the substituents of which are substituted or unsubstituted and contain no or at least one heteroatom in their chain and / or their ring;

to be selected.

16. Dual-cure polysiloxane brine according to one of claims 1 to 15, characterized in that the blocking agents for the blocked isocyanate group Y from the group consisting of

(i) phenols, such as phenol, cresol, xylenol, nitrophenol,

Chlorophenol, ethylphenol, tert-butylphenol,

Hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;

(ii) lactams, such as ε-caprolactam, δ-valerolactam, γ-

Butyrolactam or ß-propiolactam;

(iii) active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;

(iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-

Amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether,

ethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,

Propylene glycol monomethyl ether, methoxymethanol,

Glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol,

Ethylene chlorohydrin, ethylene bromohydrin, 1, 3-dichloro-2-propanol, 1, 4-cyclohexyldimethanol or acetocyanhydrin;

(v) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-

Mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;

(vi) Acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or

benzamide;

(vii) imides such as succinimide, phthalimide or maleimide;

(viii) amines, such as diphenylamine, phenylnaphthylamine, xylidine, N-

Phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;

(ix) imidazoles such as imidazole or 2-ethylimidazole;

(x) ureas, such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenyl urea;

(xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone; (xii) imines such as ethyleneimine;

(xiii) oximes, such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or

Chlorohexanonoxime;

(xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;

(xv) hydroxamic acid esters, such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or

(xvi) substituted pyrazoles and triazoles; such as

(xvii) mixtures of these blocking agents;

to be selected.

17. Dual-cure polysiloxane brine according to one of claims 1 to 16, characterized in that the non-hydrolyzable, monovalent organic radical R ^' from the group consisting of monovalent radicals which are derived from at least one of the following organic compounds:

(i) Substituted and unsubstituted, none or at least one

Heteroatoms in the chain and / or in the ring, linear or branched alkanes, alkenes, cycloalkanes,

Cycloalkenes, alkylcycloalkanes, alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes; (ii) substituted and unsubstituted aromatics or heteroamates; such as

(iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or

Alkenylcycloalkenyl-substituted aromatics or

Heteroaromatics, the substituents of which are substituted or unsubstituted and contain no or at least one heteroatom in their chain and / or their ring;

to be selected.

18. A process for the preparation of dual-cure polysiloxane sols according to any one of claims 1 to 17 by hydrolysis and condensation

(A) at least one silicon compound of the general formula

X _m Si (RY _n ) ₄ . _m (I),

where the indices and the variables have the following meaning:

m 1, 2 or 3;

n 1, 2 or 3;

X hydrolyzable residue;

R non-hydrolyzable divalent organic residue; Y blocked isocyanate group;

characterized in that before, during and / or after the hydrolysis and condensation of the hydrolyzable silicon compound I

(B) at least one compound containing at least one reactive functional group with at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive functional group;

added.

19. Use of the dual-cure polysiloxane brine according to one of claims 1 to 17 as coating materials, adhesives and

Sealing compounds for the production of coatings, adhesive layers and seals.

20. Use of the dual-cure polysiloxane brine according to one of claims 1 to 17 as a component of dual-cure coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals.

21. Use according to claim 20, characterized in that the dual-cure coating materials are dual-cure clearcoats.

22. Use according to any one of claims 19 to 21, characterized in that the coating materials, adhesives and sealants for painting, gluing and sealing motor vehicle bodies and parts thereof, motor vehicles in

Indoor and outdoor areas, buildings in indoor and outdoor areas, Doors, windows and furniture as well as in the context of industrial painting for painting, gluing and sealing small parts, coils, containers, packaging, electrical components and white goods.