CN114929932A

CN114929932A - Method for producing a component-plastic composite

Info

Publication number: CN114929932A
Application number: CN202080092080.1A
Authority: CN
Inventors: T·默克尔; J·萨博; P-M·伊格尔; G·克勒特; M·许雷尔; W·埃克勒
Original assignee: Wieland Wecotec GmbH; Robert Bosch GmbH
Current assignee: Wieland Wecotec GmbH; Robert Bosch GmbH
Priority date: 2019-11-06
Filing date: 2020-11-02
Publication date: 2022-08-19
Also published as: EP4055203A1; DE102019217123A1; WO2021089466A1

Abstract

The invention relates to a method for producing a component-plastic composite (10). In order to provide a permanently sealed and stable component-plastic composite in a cost-effective manner, in method step a), the component (11) is coated with a partially inorganic and partially organic hybrid layer (12) by means of a coating method which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, and in method step b), a resin formulation for forming a thermosetting plastic (13) is applied to the hybrid layer (12), and in method step c), the resin formulation is cured to form the thermosetting plastic (13). The invention also relates to such a component-plastic composite.

Description

Method for producing a component-plastic composite

Technical Field

The invention relates to a method for producing a component-plastic composite body and to a component-plastic composite body.

Background

Electronic and electrical lines are usually encapsulated by casting and/or by Transfer Molding (english) using thermosetting plastics, which can be formed, for example, by curing epoxy resins (EP).

However, epoxy resins are mostly produced by condensation reactions of epichlorohydrin and therefore usually contain alkali metal chlorides which promote corrosion of the metal surface. Therefore, the epoxy resin used for so-called primary overmolding, in which the epoxy resin is in direct contact with the electrical and/or electronic lines, is cumbersome to clean.

In so-called two-stage overmolding, the electronic and/or electrical lines are first coated with a thin layer of lacquer and then overmolded. However, the surfaces of most metals, such as copper and/or silver and/or aluminum and/or alloys thereof, corrode in air to form oxides, which are generally difficult to adhere to the base metal. However, this impairs the adhesion of the paint layer, so that painting only retards corrosion and oxide formation on the metal surface, but does not completely prevent them. The metal surface coated with the paint layer thus also corrodes over time, which can lead to the formation of gaps and thus to leaks between the paint and the metal surface.

Some metals, such as copper, may be protected from corrosion by an anticorrosive layer composed of a corrosion inhibitor, such as 1,2, 3-benzotriazole, triazolyl triazole or benzimidazole. However, no thermoset plastic typically adheres to such a corrosion protection layer.

The publications JP 2002-.

Disclosure of Invention

The subject of the invention is a method for producing a component-plastic composite.

The method comprises in particular a method step a) in which the component is coated with a partially inorganic and partially organic mixed layer by a coating method comprising a chemical reaction of at least one organosilicon compound as precursor and proceeding from a gas phase. In this case, the at least one organosilicon compound may be specifically designed as a precursor for forming the mixed layer.

Organosilicon compounds are understood to be, in particular, compounds having at least one, in particular direct, silicon-carbon bond (Si-C) and/or in which carbon is bonded to silicon, in particular indirectly, via at least one further element, for example via oxygen (Si-O-C) or nitrogen (Si-N-C) or sulfur (Si-S-C).

Furthermore, the method comprises, in particular, a method step b) in which a resin formulation for forming a thermosetting plastic is applied to the mixed layer. The resin formulation used to form the thermoset may specifically include or comprise a resin used to form the thermoset. The at least one resin used to form the thermoset may be, for example, a synthetic resin or a synthetic resin.

Thermosets may also be referred to as thermosets or duromers or thermosodur. Thermosetting plastics can be obtained or formed in particular by curing resin formulations, in particular resins contained in resin formulations, for example synthetic resins or synthetic resins, which are present in particular in the form of meltable solids and/or liquid or viscous and/or highly viscous materials before curing. The resin formulation and the thermoset formed therefrom may be filled or mixed with at least one filler, or may also be unfilled or unmixed, for example. After curing, the thermoset is particularly resistant to deformation.

The resin formulation and/or the resin used to form the thermoset can be applied to the mixed layer in method step b), for example in the form of a meltable solid and/or a liquid or viscous and/or highly viscous material.

Furthermore, the method comprises, inter alia, a method step c) in which the resin formulation is cured or is cured to a thermoset. In particular, the resin of the resin formulation can be cured or cured.

In this way, a component-plastic composite can be formed.

The coating process, which comprises a chemical reaction of at least one organosilicon compound as precursor and which proceeds from a gaseous phase, advantageously makes it possible to form particularly thin, partially inorganic and partially organic hybrid layers which act as adhesion promoters, in particular between the component and the thermosetting plastic, have good adhesion properties to the thermosetting plastic and are both particularly sealable, for example water-proof, in particular moisture-proof, even possibly gas-tight, and particularly stable, in particular hydrolysis-resistant. Since the partially inorganic and partially organic mixed layer formed in this way has high hydrolysis resistance, it is also possible to favorably maintain its adhesive properties, impermeability and stability for a long period of time, and also to protect the member from corrosion.

Furthermore, by the coating method according to the invention, for example, the use of solutions and/or dispersions and/or emulsions which, on coating complex structures and/or contours, lead to the formation of inhomogeneous layers as a result of capillary forces, it may also be advantageous to coat components having an uneven surface, for example having a complex structure and/or having a complex contour, in particular components having an uneven, in particular complex-structured and/or complex-shaped metal surface, in particular a component having a surface with at least one at least partially concave curvature and/or at least one surface with at least one concave edge and/or at least one concave corner, with a uniform, thin and dense, in particular a mixed layer of partly inorganic and partly organic which is also uniformly stable and resistant to hydrolysis, in particular promotes adhesion.

The coating method, by which, in particular in method step a), a partially inorganic and partially organic mixed layer containing silicon and oxygen can be formed, comprises a chemical reaction of at least one organosilicon compound as a precursor and is carried out from a gas phase.

The coating process, by means of which, in particular in process step a), for example, a partially inorganic and partially organic mixed layer can be formed, which comprises siloxane structures and/or, for example, amorphous silicon dioxide based thereon, possibly formed therefrom, comprises a chemical reaction of at least one organosilicon compound as a precursor and is carried out from a gas phase.

The coating process, by which, in particular in process step a), a partially inorganic and partially organic mixed layer can be formed, which has a siloxane structure and/or a silsesquioxane structure and/or amorphous silica, for example based thereon, possibly formed therefrom, comprises a chemical reaction of at least one organosilicon compound as precursor and is carried out from a gas phase.

The coating process comprises a chemical reaction of at least one organosilicon compound as precursor and is carried out from a gas phase, by which, in particular in process step a), it is possible, for example, to form organic-inorganic hybrid polymers from at least one organosilicon compound, which hybrid polymers have siloxane structures and/or silsesquioxane structures and/or regions of amorphous silica.

SilsesquioxanesIn particular, siloxanes having a cage-like and/or polymeric or oligomeric structure based on silicon-oxygen-silicon bridges (-Si-O-Si-) and tetrahedral silicon vertices are to be understood. For example, the silsesquioxane may comprise the general chemical formula- [ SiO _1, ₅ X] _n Siloxane units of (a) and (b), in particular based on the siloxane units, wherein n is the number of the siloxane units and X may, for example, be an organic group, hydrogen, halogen or other substituent which may be terminated or optionally also bridged and/or linked. The silsesquioxanes may be designed polymeric or oligomeric and/or cage-like. Polymeric silsesquioxanes may for example have a random and/or ladder-like and/or cage-like basic structure. The cage silsesquioxanes may in particular have a cage-like basic structure consisting of a plurality of siloxane units per cage, for example [ SiO ] SiO _1.5 R]Unit formation, e.g. up to 18 siloxane units per cage, e.g. up to 18 [ SiO ] _1.5 R]-a unit. Furthermore, the cage silsesquioxanes may be linked to one another oligo-or multimerically and may therefore be both cage-like and oligo-or multimerically. An example of a cage silsesquioxane is octapolysilsesquioxane having the form of an octahedral cage consisting of 8 siloxane units, e.g., 8 [ SiO ] _1.5 R]A basic structure of units and may also be connected oligo-or poly-merically, for example, polyactahedral silsequioxanes (POSS; English: Polyoctohedral Silsoquioxanes). Another example of a caged silsesquioxane is a tenfold silsesquioxane having a basic structure in the form of a cage consisting of 10 siloxane units, e.g. 10 [ SiO ] s _1.5 R]-units and can also be connected oligo-or poly-merically.

Silicon-oxygen structural elements, such as siloxane structures and/or silsesquioxane structures and/or amorphous silicon dioxide, may form, inter alia, the inorganic part of the hybrid layer.

The organic component and/or the organic reaction product of the at least one organosilicon compound and/or the organic group resulting from a silicon-oxygen structural element formed from the at least one organosilicon compound, for example a silicon atom of a siloxane and/or silsesquioxane structure, may especially form the organic part of the mixed layer.

Since the partially inorganic and partially organic hybrid layer can be particularly sealed, for example liquid-tight, for example water-tight, in particular moisture-tight, possibly even gas-tight, and stable, in particular also particularly hydrolysis-resistant, the component can advantageously, in particular also over a long period, be protected from environmental influences, for example water, in particular also moisture, and possibly also gases and other surrounding media, and also from corrosion and dust, and/or such substances can be contained in the component.

Since the hybrid layer already protects the component from the environment, the component coated with the hybrid layer does not have to be further processed directly in method step b), which is advantageous for mass production.

Since the partially inorganic and partially organic mixed layer has good adhesion properties to the thermosetting plastic, good adhesion of the thermosetting plastic to the mixed layer can advantageously be achieved.

Since the resin formulation is applied to the partially inorganic and partially organic hybrid layer and cured to form the thermosetting plastic, the component can advantageously be protected better, in particular also permanently, from environmental influences, such as water, in particular also moisture, and possibly also from gases and other media, for example also from dust, and/or such substances are better contained in the component. Furthermore, the components and the mixed layer can be protected from mechanical influences by the thermosetting plastic. By using a thermoset, these advantages can also be maintained for a longer period of time than with other plastics (e.g., thermoplastics). This is possible because the shrinkage which occurs when the resin formulation cures to a thermoset is much smaller, for example, compared to the thermoplastic curing, and the thermoset can have a lower tendency to swell than the other plastics, whereby internal stresses can be reduced and/or avoided and in this way permanent adhesion, impermeability and stability of the component plastic composite can be achieved.

Furthermore, thermosets can be made from inexpensive materials. In addition, at higher wall thicknesses of the resin formulations used to form the thermoset plastics, their hardening can occur more rapidly than the solidification of the thermoplastic melt. Both of these can in turn have a favorable influence on the economics of the production process. By means of the mixed layer and the thermosetting plastic, the component can advantageously be encapsulated in a sealing manner, in particular permanently. The component-plastic composite can thus be designed, for example, as a sealed package.

Overall, a permanently sealed, for example waterproof and/or moisture-proof and/or gas-tight and stable component-plastic composite can then be provided in a cost-effective manner.

The partially inorganic and partially organic mixed layer formed in method step a) may comprise, in particular, silicon and oxygen. For example, the partially inorganic and partially organic mixed layer formed in method step a) may comprise siloxane structures and/or amorphous silicon dioxide, for example siloxane structures and/or silsesquioxane structures and/or amorphous silicon dioxide, for example based thereon, optionally formed therefrom. For example, the partially inorganic and partially organic hybrid layer formed in method step a) may comprise, for example on the basis thereof, an organic-inorganic hybrid polymer having siloxane structures and/or silsesquioxane structures and/or amorphous silica regions, optionally formed therefrom.

The coating process carried out in process step a) can be, in particular, chemical vapor deposition, which comprises a chemical reaction of at least one organosilicon compound as precursor and is carried out from a gas phase.

Thus, within the scope of one embodiment, the coating in method step a) is carried out by chemical vapor deposition, in particular from a gas phase comprising at least one organosilicon compound as precursor (in particular for forming a mixed layer).

For example, in method step a), one or the component can be coated by chemical vapor deposition from a vapor phase comprising at least one organosilicon compound as precursor, with one or the partially inorganic and partially organic mixed layer. The chemical vapor deposition can be carried out in particular at atmospheric pressure.

By chemical vapour deposition from a vapour phase comprising at least one organosilicon compound as precursor, it is advantageously possible to form in a simple manner, in particular from a silicon-and oxygen-containing, partially inorganic and partially organic mixed layer which can be particularly sealed, for example both water-and moisture-tight, possibly even gas-tight, and particularly hydrolysis-resistant, and which comprises, for example, siloxane structures and/or silsesquioxane structures and/or amorphous silicas, for example organic-inorganic mixed polymers having siloxane structures and/or silsesquioxane structures and/or amorphous silica domains, and/or based on and/or formed from them. Furthermore, by means of chemical vapor deposition, in which the reaction is activated without plasma, it is advantageously possible to obtain a more uniform layer than by means of a plasma method in which, due to the effect of the electric field, disadvantageous layer elevations occur at the corners and edges.

The coating process, which comprises a chemical reaction of at least one organosilicon compound as precursor and a chemical vapor deposition from a gaseous phase, for example from a gaseous phase comprising at least one organosilicon compound as precursor, also advantageously enables the formation of a partially inorganic and partially organic mixed layer having at least one functional group, in particular using at least one organosilicon compound having at least one functional group as precursor, in particular even at elevated temperatures, for example of about 300 ℃, in such a way that the at least one functional group can remain on the partially inorganic and partially organic mixed layer even after the end of the coating process.

This has not been possible to date using conventional coating methods.

In conventional coating processes, in which layers are formed by applying organosilanes from solution and drying these at low temperatures, in particular only organic layers are formed which, although they may be provided with functional groups and may initially have good adhesion properties, are devoid of inorganic components, for example in the form of-Si-O-Si-units, for example in the form of siloxane structures and/or silsesquioxane structures and/or amorphous silica, and in the case of inadequate crosslinking of themselves and of metal surfaces, generally have a lower hydrolysis resistance and do not provide corrosion protection, so that initially good adhesion properties are generally lost under the action of moisture here.

In other conventional coating processes, in which layers are formed by applying organosiloxane lacquers and these are baked in air, inorganic layers are formed which, although resistant to hydrolysis and can provide corrosion protection, are also used as mold release agents in plastic molding dies because of the lack of organic constituents, in particular because of the lack of functional groups, which generally have poor adhesion properties. During the baking in air, the functional groups are thereby destroyed by oxidation, so that the layer produced in this way no longer has any functional groups after baking.

Within the scope of a further embodiment, therefore, in method step a), a partially inorganic and partially organic mixed layer having at least one functional group is formed. For example, in method step a), one or the component having one or the partially inorganic and partially organic hybrid layer having at least one functional group is coated by a coating process, for example by chemical vapor deposition from a gas phase comprising at least one organosilicon compound as precursor, which coating process comprises a chemical reaction of at least one organosilicon compound as precursor and from a gas phase.

In this case, the coating in process step a) can be carried out in particular with or from a gas phase which comprises at least one organosilicon compound having at least one functional group as a precursor, in particular for forming a mixed layer.

Since the partially inorganic and partially organic hybrid layer formed in method step a) is provided with at least one functional group, it is advantageously possible to react at least one functional group of the hybrid layer with at least one functional group of the resin formulation and to form a covalent bond between the hybrid layer and the thermosetting plastic formed in particular from the resin formulation. The covalent bond may be at least 10 times stronger than the pure adhesion (physisorption). A particularly strong and particularly hydrolysis-resistant connection of the thermosetting plastic to the mixed layer can then be achieved, which can be significantly stronger in particular than a purely physical adhesion. This makes it possible to achieve a particularly durable, strong and tight joint between the component, the mixed layer and the thermosetting plastic.

Within the scope of a further embodiment, the resin formulation in method step b) therefore comprises a resin having at least one repeating unit which has at least one, in particular covalently bonded, functional group. In particular, a covalent bond can be formed between the mixed layer and the thermosetting plastic, in particular made of a resin, in particular by reaction of at least one functional group of the mixed layer with at least one functional group of at least one repeating unit of the resin.

Within the scope of one embodiment, the coating in process step a) is carried out at a temperature in the range from ≥ 200 ℃ to ≤ 400 ℃. For example, the coating in process step a) can be carried out at a temperature in the range from ≥ 250 ℃ to ≤ 350 ℃. This has proven to be particularly advantageous for the formation of partially inorganic and partially organic mixed layers, which in particular have at least one functional group. Such coating temperatures may be relatively low compared to coating temperatures of other coating methods, such as for forming a silicon dioxide layer. Advantageously, such a coating temperature may be low enough to allow, for example, coating of printed circuit boards that are already equipped with electronic devices. In method step a), such a coating temperature can be achieved, for example, by the so-called semi-hot-wire method or by the so-called hot-wall method.

Within the scope of a further embodiment, the gas phase in process step a) is a reducing or inert gas phase. In particular, the gas phase in process step a) may be a reduced gas phase. For example, the gas phase in process step a) may comprise hydrogen, for example a nitrogen-hydrogen mixture, such as nitrogen and/or argon and hydrogen. In this way, at least one functional group of the mixed layer or of the at least one organosilicon compound can advantageously be protected from oxidation.

Within the scope of a further embodiment, the gas phase in process step a) comprises at least one acid and/or water, in particular at least one bronsted acid, for example at least one carboxylic acid, such as acetic acid. The chemical reaction of the at least one organosilicon compound in the gas phase during the coating process, for example in chemical vapor deposition, can advantageously be catalyzed and/or accelerated by the at least one acid, in particular a Bronsted acid, for example a carboxylic acid. For example by means of at least one acid, in particular a bronsted acid, such as a carboxylic acid, and/or by means of water.

Within the scope of one embodiment, the coating in method step a) is carried out during the coating process, for example in chemical vapor deposition, at a temperature in the range of the favorable silicon-oxygen-carbon bond (Si-O-C) of the organosilicon compound in the vapor phase, is partially hydrolyzed to silane (Si-O-H), which in turn can be partially bonded to the surface of the component and, in the case of partial dehydration, can be condensed, for example, to siloxane (-Si-O-Si-) and/or structures composed of silicon dioxide, in particular amorphous silicon dioxide. In the partially inorganic and partially organic mixed layer formed in this case, the oxygen can in this case originate partly from the water contained in the gas phase. The dissociation properties as well as the catalytic properties of at least one acid, in particular a bronsted acid such as a carboxylic acid, can also be advantageously enhanced by water.

In particular, the gas phase in process step a) may thus comprise at least one acid and water, in particular at least one bronsted acid, for example at least one carboxylic acid, for example acetic acid. A particularly rapid formation of the partially inorganic and partially organic hybrid layer can thus be achieved. The presence of at least one acid and water here may in particular support the inorganic components forming the hybrid layer, for example in the form of-Si-O-Si units, for example in the form of siloxane structures and/or silsesquioxane structures and/or amorphous silicon dioxide. This has also proven to be particularly advantageous for coating components having an uneven surface, for example components having a complex structure and/or complex shape, in particular components having an uneven, in particular complex structured and/or complex shaped metal surface.

Within the scope of a further embodiment, the at least one functional group of the mixed layer and/or of the at least one organosilicon compound comprises or is, in particular, an unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond, and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiocarbamate group and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group (-O-C ≡ N) and/or an isocyanate group (-N ═ C ≡ O) and/or a thiocyanate group (-S-C ≡ N) and/or an isothiocyanate group (-N ≡ C ≡ S) and/or a nitrile group (-C ≡ N). These functional groups may facilitate the formation of covalent bonds with the functional groups of the resin.

Thiocarbamate groups, which may also be referred to as thiourethane groups, are understood in particular as the following groups: in this group, the nitrogen atom is bonded to a carbon atom, and the carbon atom is in turn bonded to at least one sulfur atom. Here, the carbon atom is in particular still bonded to an oxygen atom (-N-CS-O-) or to another sulfur atom (-N-CS-S-).

Within the scope of a special design of this embodiment, at least one functional group of the hybrid layer and/or of the at least one organosilicon compound comprises or is a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of, in particular, a single or separate vinyl group, and/or in the form of a vinyl group, for example an allyl group, which is bonded to a bridging group, and/or a vinylidene group and/or an amino group and/or a hydroxyl group, and/or a thiol group and/or a thiourethane group and/or a dithiourethane group and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group and/or an isocyanate group and/or a thiocyanate group and/or an isothiocyanate group and/or a nitrile group. These functional groups are particularly advantageous for forming covalent bonds with the functional groups of the resin.

Vinylidene groups are understood to mean, in particular, bridged, substituted or unsubstituted vinylidene groups. For example, vinylidene groups may be based on the general chemical formula: -CR ═ CR —, wherein R and R may each independently represent hydrogen or a substituent, in particular hydrogen.

A thiocarbamate group is to be understood in particular as a thiocarbamate group, in which a carbon atom is bound to a sulfur atom by a double bond and to an oxygen atom by a single bond. For example, the thiourethane group may be based on the general chemical formula: -NR-CS-O-R, wherein R and R may each independently represent hydrogen or a substituent, in particular hydrogen.

A thiourethane group is understood to mean, in particular, a thiocarbamate group in which a carbon atom is bonded to an oxygen atom by a double bond and to a sulfur atom by a single bond. For example, a thiourea alkyl group can be based on the general chemical formula: -NR-CO-S-R, wherein R and R may each independently represent hydrogen or a substituent, in particular hydrogen.

A dithiocarbamate group is understood to be, in particular, a thiocarbamate group in which a carbon atom is bonded to a sulfur atom by a double bond and to another sulfur atom by a single bond. For example, the dithiocarbamate group can be based on the general chemical formula: -NR-CS-S-R, wherein R and R may each independently represent hydrogen or a substituent, in particular hydrogen.

The at least one functional group of the mixed layer may, for example, comprise and optionally correspond to at least one functional group of the at least one organosilicon compound and/or comprise and optionally correspond to a decomposition product of at least one functional group of the at least one organosilicon compound.

For example, the at least one functional group of the at least one organosilicon compound may comprise or be in particular an unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond, such as a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of an in particular single or individual vinyl group, and/or in the form of a vinyl group, such as an allyl group, which is bonded to a bridging group, and/or comprise or be in the form of a vinylene group and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiocarbamate group, such as a thiourethane group and/or a thiourea group and/or a dithiocarbamate group and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group and/or an isocyanate group and/or a thiocyanate group and/or an isocyanate group A thiocyanate group and/or a nitrile group.

Unsaturated functional groups of the organosilicon compounds, in particular having at least one free-radically polymerizable carbon-carbon double bond, for example methacrylate groups and/or acrylate groups and/or vinyl groups and/or allyl groups and/or vinylene groups, and/or amino groups and/or hydroxyl groups and/or thiol groups and/or thiocarbamate groups, for example thiourethane groups and/or thiourea groups and/or dithiourethane groups, and/or carboxylic acid groups and/or epoxide groups, can advantageously be relatively stable per se and remain at least substantially intact in the coating in process step a). Thus, when at least one organosilicon compound having at least one such functional group is used, the mixed layer may also comprise at least one corresponding functional group.

The cyanate groups (-O-C.ident.N) of the organosilicon compounds can be decomposed in the coating in process step a), for example, into hydroxyl groups. Thus, when at least one organosilicon compound having at least one cyanate group is used, the mixed layer may include at least one hydroxyl group.

In the coating in method step a), the isocyanate groups (-N ═ C ═ O) of the organosilicon compounds can be hydrolyzed, for example, to carbamic acid (-NH — COOH), which can then be decomposed to amino groups. Thus, when at least one organosilicon compound having at least one isocyanate group is used, the mixed layer may comprise at least one amino group.

The thiocyanate groups (-S-C N) of the organosilicon compounds can be decomposed in the coating in method step a), for example, into thiol groups. Thus, when at least one organosilicon compound having at least one thiocyanate group is used, the mixed layer may comprise at least one thiol group.

The isothiocyanate groups (-N ═ C ═ S) of the organosilicon compounds can be decomposed in the coating in process step a), for example, into thiourethane groups, such as thiourethane groups and/or thiourea alkyl groups. Thus, when at least one organosilicon compound having at least one isothiocyanate group is used, the mixed layer may comprise at least one thiourethane group, such as a thiourethane group and/or a thiourethane group.

The nitrile groups (-CN) of the organosilicon compound can be decomposed in the coating in method step a), for example, to carboxylic acid groups. Thus, when at least one organosilicon compound having at least one nitrile group is used, the mixed layer may comprise at least one carboxylic acid group.

The at least one functional group of the hybrid layer may thus, for example, comprise or be, in particular, an unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond, such as a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of one, in particular a single or separate, vinyl group, and/or in the form of a vinyl group, for example an allyl group, and/or an allyl group and/or a vinylene group, and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiocarbamate group, such as a thiocarbamate group and/or a thiourea group and/or a dithiocarbamate group, and/or a carboxylic acid group and/or an epoxide group, connected to a bridging group.

The unsaturated functional groups on the mixed layer can advantageously react with the unsaturated functional groups on the resin, in particular a radical reaction, for example an addition reaction, and in this way form covalent bonds between the mixed layer and the thermosetting plastic formed from the resin.

The amino groups and/or hydroxyl groups and/or thiol groups and/or carboxylic acid groups and/or epoxide groups on the mixed layer can advantageously undergo an addition reaction with epoxide groups on the resin and in this way form covalent bonds between the mixed layer and the thermoset formed from the resin.

The hydroxyl groups on the hybrid layer or on the resin can advantageously also undergo esterification or condensation reactions with carboxylic or amino groups and hydroxyl and/or thiol groups on the resin or hybrid layer and in this way form covalent bonds between the hybrid layer and the thermoset formed from the resin.

The thiourethane groups, such as thiourethane groups and/or thiourea groups and/or dithiocarbamate groups, on the mixed layer can advantageously react with the amine groups of the resin and in this way form covalent bonds between the mixed layer and the thermoset formed from the resin.

In addition, the amino group can favorably accelerate the reaction in the gas phase and achieve a higher film formation rate. The reaction time can then advantageously be shortened, or a larger layer thickness can be achieved without shortening the reaction time than in the absence of amino groups. In addition, the amino group built in the mixed layer can increase the elasticity of the mixed layer, thereby increasing the mechanical strength thereof.

Furthermore, thiol groups can form stable metal-sulfur bonds with certain metals (e.g., copper and/or silver). As a result, the adhesion of the mixed layer on the metal surface of the component (e.g. made of copper and/or silver) can be advantageously increased. Furthermore, the thiol group can advantageously be modified synthetically afterwards and in this way the properties of the mixed layer can be changed.

In addition, carboxylic acid groups can advantageously improve the corrosion resistance of metals.

Furthermore, the thiourethane groups can also form stable metal-sulfur bonds with certain metals, such as copper and/or silver. As a result, the adhesion of the mixed layer on the metal surface of the component (e.g. made of copper and/or silver) can be advantageously increased. Furthermore, better crosslinking within the mixed layer can advantageously be achieved by the thiourethane groups. Furthermore, the thiocarbamate group can advantageously be modified synthetically afterwards and in this way the properties of the hybrid layer can be changed.

Within the scope of another embodiment, the at least one organosilicon compound comprises an organosilane. In particular, the at least one organosilicon compound may be an organosilane.

Organosilane is understood to mean, in particular, a compound which comprises at least one, in particular direct, silicon-carbon bond (Si — C).

Within the scope of a further embodiment, at least one functional group of the mixed layer and/or of the at least one organosilicon compound is bonded to silicon via a silicon-carbon bond (Si — C). A hydrolysis-resistant connection of the at least one functional group to the silicon and thus to the mixed layer can then advantageously be achieved. As a result, a hydrolysis-resistant connection of the thermosetting plastic to the mixed layer can advantageously be achieved. The at least one organosilicon compound having at least one functional group can in particular be an organosilane here.

In addition to at least one functional group which is bonded to silicon, in particular via a silicon-carbon bond (Si-C), alkoxy groups, such as methoxy and/or ethoxy and/or propoxy and/or butoxy groups, can be bonded to the silicon of at least one organosilicon compound having at least one functional group.

The at least one organosilicon compound having at least one functional group may comprise or be at least one vinylsilane, such as triethoxyvinylsilane and/or trimethoxyvinylsilane and/or tris (2-methoxyethoxy) vinylsilane, and/or at least one allylsilane, for example as allyltrimethoxysilane and/or at least one methacrylic acid-or acrylate silane, for example at least one methacrylic acid-or acrylate silane, such as 3-trimethoxysilylpropyl methacrylate and/or (3-acryloyloxypropyl) trimethoxysilane, and/or at least one aminosilane, for example at least one aminoalkylsilane such as (3-aminopropyl) trimethoxysilane and/or bis (3-triethoxysilylpropyl) amine and/or N- [3- (tris-triethoxysilylpropyl) amine Methoxysilyl) propyl ] butylamine and/or tris (dimethylamino) silane and/or N- [3- (dimethoxymethylsilyl) propyl ] ethylenediamine, and/or at least one mercaptosilane, for example at least one mercaptoalkylsilane, for example 3-mercaptopropyltrimethoxysilane, and/or at least one glycidoxysilane, for example at least one glycidoxyalkylsilane, such as (3-glycidoxypropyl) trimethoxysilane, and/or at least one isocyanatosilane, for example at least one isocyanatoalkylsilane, for example 3-isocyanatopropyltrimethoxysilane, and/or at least one thiocyanatosilane, for example at least one thiocyanatoalkylsilane, for example 3-thiocyanatopropyltriethoxysilane, and/or at least one cyanosilane, for example at least one cyanoalkylsilane, for example (3-cyanopropyl) dimethylchlorosilane.

In a special design of this embodiment, the at least one organosilicon compound having at least one functional group comprises or is triethoxyvinylsilane and/or trimethoxyvinylsilane and/or allyltrimethoxysilane and/or tris (2-methoxyethoxy) vinylsilane and/or 3-trimethoxysilylpropyl methacrylate and/or (3-acryloyloxypropyl) trimethoxysilane. In particular, the at least one organosilicon compound having at least one functional group may comprise or be triethoxyvinylsilane and/or trimethoxyvinylsilane and/or allyltrimethoxysilane and/or tris (2-methoxyethoxy) vinylsilane.

Within the scope of a further embodiment, the gas phase in method step a) also comprises at least one further organosilicon compound as a precursor, in particular for forming a hybrid layer. In this way, the properties of the mixed layer can advantageously be set in a targeted manner.

Within the scope of one design of this embodiment, the gas phase in method step a) also comprises at least one further organosilicon compound having at least one further functional group as a precursor, in particular for forming a mixed layer. Here, the at least one further functional group can, for example, modify the properties of the hybrid layer and/or improve, for example, the coating process and/or can react or react with the at least one functional group of the at least one organosilicon compound and/or with the at least one functional group of the at least one repeating unit of the resin to form a covalent bond.

The stability and/or impermeability and/or hydrolysis resistance of the hybrid layer can advantageously be further increased by forming a covalent bond between the at least one further functional group of the at least one further organosilicon compound and the at least one functional group of the at least one organosilicon compound.

The bonding of the thermosetting plastic to the hybrid layer and/or the hydrolysis resistance of the bonding can advantageously be further improved by forming a covalent bond between the at least one further functional group of the at least one further organosilicon compound and the at least one functional group of the at least one repeating unit of the resin.

The at least one further organosilicon compound having at least one further functional group can in particular likewise be an organosilane. The at least one further functional group can be bonded to silicon, in particular via a silicon-carbon bond (Si — C).

The at least one further functional group may here comprise or be, for example, an unsaturated functional group, in particular with at least one free-radically polymerizable carbon-carbon double bond, such as a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of a vinyl group, in particular singly or individually, and/or in the form of a vinyl group, for example an allyl group, which is bonded to a bridging group, and/or a vinylene group and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiocarbamate group, for example a thiourethane group and/or a dithiourethane group, and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group and/or an isocyanate group and/or a thiocyanate group and/or an isothiocyanate group and and/or a nitrile group.

The at least one further functional group of the at least one further organosilicon compound can in particular be different from the at least one functional group of the at least one organosilicon compound.

Within the scope of a special design of this embodiment, the at least one organosilicon compound having at least one functional group comprises, as functional groups, methacrylate groups and/or acrylate groups, in particular methacrylate groups. The at least one further organosilicon compound having at least one further functional group here comprises, as further functional groups, amino groups and/or isocyanate groups, for example amino groups. The at least one organosilicon compound having at least one functional group and the at least one further organosilicon compound having at least one further functional group can be designed here, in particular, in the form of organosilanes. This has proven to be particularly advantageous for the long-term impermeability and stability of the hybrid layer and for the long-term adhesion properties of the hybrid layer.

For example, the at least one organosilicon compound having at least one functional group may comprise or be (3-trimethoxysilylpropyl methacrylate and/or (3-acryloxypropyl) trimethoxysilane, and the at least one other organosilicon compound having at least one other functional group may comprise or be (3-aminopropyl) trimethoxysilane and/or bis (3-triethoxysilylpropyl) amine and/or N- [3- (trimethoxysilyl) propyl ] butylamine and/or tris (dimethylamino) silane and/or N- [3- (dimethoxymethylsilyl) propyl ] ethylenediamine.

The mixed layer can in particular have a reaction product from an addition reaction, in particular a michael addition, of one or the amino groups with methacrylate groups and/or acrylate groups. For example, the reaction product may be a 4-Aza (Aza) -2-heptanoic acid propyl ester group:

furthermore, the gas phase in process step a) may, for example, also comprise as precursor at least one unfunctionalized organosilicon compound, i.e. an organosilicon compound without functional groups. The at least one non-functionalized organosilicon compound can be, for example, a symmetrical or asymmetrical silicate, in particular a symmetrical silicate.

Within the scope of a further, alternative or additional embodiment, the gas phase in process step a) also comprises at least one, for example, symmetrical or asymmetrical, in particular symmetrical, silicate. By using at least one silicate, the silica content of the mixed layer can be advantageously increased. In this way, the properties of the mixed layer can be specifically adjusted.

In particular, the gas phase in process step a) may also comprise at least one, for example symmetrical or asymmetrical, in particular symmetrical, orthosilicate.

Within the scope of one design of this embodiment, the at least one silicate, in particular orthosilicate, comprises or is at least one silicate, in particular orthosilicate, having the following chemical formula:

here, R10, R11, R12 and R13 may each independently represent an alkyl group, such as a methyl or ethyl group or a propyl group, such as a n-propyl or isopropyl group, or a butyl group, such as a n-butyl or isobutyl group or a tert-butyl group.

For example, the at least one silicate, in particular an orthosilicate, may comprise or be tetraethyl orthosilicate (TEOS) and/or tetrapropyl orthosilicate (TPOS) and/or tetramethyl orthosilicate (TMOS). By using tetraethyl orthosilicate (TEOS) and/or tetrapropyl orthosilicate (TPOS), process reliability can be advantageously improved compared to tetramethyl orthosilicate.

In particular, the at least one silicate may comprise or be an orthosilicate, in particular tetramethyl orthosilicate (TMOS) and/or tetraethyl orthosilicate (TEOS).

Within the scope of a further embodiment, the gas phase in process step a) also comprises at least one unfunctionalized organosilicon compound, in particular at least one, for example, symmetrical or asymmetrical, in particular symmetrical, silicate. In particular, the concentration of the at least one organosilicon compound having at least one functional group and/or the concentration of the at least one further organosilicon compound having at least one further functional group can be increased and/or the concentration of the at least one non-functionalized organosilicon compound can be reduced in the gas phase during process step a).

Advantageously, non-functionalized organosilicon compounds, such as silicates, can bond particularly well to metal surfaces, wherein no functional groups are required for this purpose. By increasing the concentration of at least one organosilicon compound having at least one functional group and/or the concentration of at least one other organosilicon compound having at least one other functional group and/or decreasing the concentration of at least one non-functionalized organosilicon compound in the gas phase during process step a), the precursor having functional groups matching the resin formulation is metered into the gas phase over the coating time, so that the functional groups are predominantly bound to the surface of the coating, which is then brought into contact with the resin formulation. The advantageous properties of the hybrid layer, in particular with regard to adhesion promotion and corrosion protection and/or impermeability, can then be further improved.

In particular, the concentration of at least one functional group and/or at least one further functional group and/or their decomposition products can increase from the component towards the surface of the mixed layer to be coated with the resin formulation. A partially inorganic and partially organic mixed layer can then advantageously be formed, the organic proportion increasing in the direction from the component to the thermosetting plastic. Such a gradient in the composition of the partially inorganic and partially organic mixed layer can result from the above-described process control in method step a), in which the precursor concentration in the gas phase changes over time.

Prior to the coating in method step a), the component can optionally be cleaned, for example in method step a0), for example degreased and/or pickled and/or washed, and/or dried and/or heat treated, for example in an atmosphere of a nitrogen-hydrogen mixture.

Within the scope of a further embodiment, the resin formulation used, in particular in process step b), comprises an unsaturated polyester resin and/or a vinyl ester resin and/or an epoxy resin.

In particular, the at least one resin may comprise or be an unsaturated polyester resin and/or a vinyl ester resin and/or an epoxy resin. Thermosets based on these resins may advantageously have a tendency to swell to a negligible extent, in particular under the influence of moisture and possibly also under the influence of other media. Internal stresses caused by swelling, which may lead to a reduction in adhesion, impermeability and stability, can then be avoided. Furthermore, thermosets based on these resins have a high resistance to hydrolysis and/or media. This is particularly advantageous for the permanent adhesion, permanent impermeability and permanent stability of the composite.

Epoxy resins are also characterized by low (reaction) shrinkage when cured into thermoset plastics.

In particular, the resin formulation may comprise an unsaturated polyester resin and/or a vinyl ester resin. For example, the resin may comprise or be an unsaturated polyester resin and/or a vinyl ester resin. Compared to epoxy resins, unsaturated polyester resins and vinyl ester resins can contain significantly less or even almost no or no production-induced ionic impurities and/or are significantly cheaper. The (reaction) shrinkage of resin formulations based on unsaturated polyester resins and vinyl ester resins, although possibly higher per se than that of resin formulations based on epoxy resins, can advantageously be reduced to zero or even to less than zero by adding shrinkage reducing agents, so-called low profile additives.

For example, the resin formulation may include a vinyl ester resin.

In particular, the resin can comprise or be a vinyl ester resin.

Vinyl ester resins are more resistant to hydrolytic degradation than polyester resins.

Within the scope of a further embodiment, at least one functional group of at least one repeating unit of the resin comprises or is an unsaturated functional group, in particular having at least one free-radically polymerizable carbon-carbon double bond, for example a methacrylate group and/or an acrylate group and/or a vinylene group, and/or an epoxide group and/or a hydroxyl group.

In the case of resins having repeating units with unsaturated functional groups, in particular with at least one free-radically polymerizable carbon-carbon double bond, at least one functional group of the hybrid layer can in particular be an unsaturated functional group, in particular with at least one free-radically polymerizable carbon-carbon double bond, for example a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of one, in particular a single or separate, vinyl group, and/or in the form of a vinyl group, for example an allyl group, which is linked to a bridging group, and/or a vinylidene group.

By reacting at least one unsaturated functional group of the mixed layer, in particular having at least one free-radically polymerizable carbon-carbon double bond, with at least one unsaturated functional group of the resin, in particular having at least one free-radically polymerizable carbon-carbon double bond, alkyl units can be formed, by means of which a covalent bond can advantageously be formed between the mixed layer and the thermosetting plastic formed from the resin.

In the case of resins having repeating units bearing epoxide groups, at least one functional group of the hybrid layer may comprise or be in particular an amino group and/or a hydroxyl group and/or a thiol group and/or a carboxylic acid group and/or an epoxide group.

The epoxy group can react with the amino group, for example, to form a secondary or tertiary amine unit bridged by a covalent bond. In particular, the hydroxyl group can be formed here on a carbon atom adjacent to the carbon atom substituted by the amine group.

For example, an epoxy group can react with a hydroxyl group, particularly by an addition reaction, to form an ether unit bridged by a covalent bond. In particular, the hydroxyl group can be formed here on a carbon atom adjacent to the carbon atom substituted by an ether group.

For example, an epoxy group may react with a thiol group, in particular by an addition reaction, to form a thioether unit (R-S-R) bridged by a covalent bond. In particular here, the hydroxyl group can be formed on a carbon atom adjacent to the carbon atom substituted by the thioether unit.

For example, an epoxy group may react with a carboxylic acid group, particularly by an addition reaction, to form a carboxylate unit bridged by a covalent bond. In particular, the hydroxyl group can be formed here on a carbon atom adjacent to the carbon atom substituted by the carboxylate unit.

For example, the epoxy groups may react with the epoxy groups to form ether units bridged by covalent bonds, or to polymerize into polyethers.

By means of a reaction, in particular an addition reaction, of at least one epoxide group of the resin with an amino group and/or a hydroxyl group and/or a thiol group and/or a carboxylic acid group and/or an epoxide group of the hybrid layer, a covalent bond can then advantageously be formed between the hybrid layer and the thermoset formed from the resin.

In the case of resins having repeating units with hydroxyl groups, at least one functional group of the hybrid layer may in particular comprise or be an epoxy group and/or a carboxylic acid group and/or a thiol group.

By reaction, in particular addition reaction or esterification reaction or condensation reaction, of the hydroxyl groups of the resin with the epoxy and/or carboxylic acid groups and/or thiol groups of the mixed layer, ether units or carboxylate units can be formed, by means of which covalent bonds can advantageously be formed between the mixed layer and the thermoset formed from the resin.

Within the scope of a further embodiment, the resin having at least one repeating unit with at least one functional group comprises or is an unsaturated polyester resin and/or a vinyl ester resin and/or an epoxy resin. These resins may advantageously have at least one repeating unit bearing at least one functional group that can react with at least one functional group of the hybrid layer to form a covalent bond.

Within the scope of one design of this embodiment, the resin, in particular the resin having at least one repeating unit with at least one functional group, comprises or is an unsaturated polyester resin (UP resin).

Unsaturated polyester resins are to be understood as meaning, in particular, resins, especially synthetic resins or synthetic resins, which comprise, in particular, oligomeric or polymeric condensation products of at least one diol with at least one dicarboxylic acid, have at least one free-radically polymerizable carbon-carbon double bond and/or have at least one dicarboxylic anhydride with at least one free-radically polymerizable carbon-carbon double bond. Such condensation products may also be referred to as unsaturated polyesters, in particular having at least one free-radically polymerizable carbon-carbon double bond.

The condensation products or unsaturated polyesters can in particular be produced or obtainable by condensation, for example polycondensation, of at least one diol, for example 1, 2-propanediol and/or ethylene glycol and/or diethylene glycol and/or 1, 3-butanediol and/or 1, 4-butanediol, with at least one dicarboxylic acid having at least one free-radically polymerizable carbon-carbon double bond, for example maleic acid and/or tetrahydrophthalic acid and/or fumaric acid, and/or with at least one dicarboxylic anhydride having at least one free-radically polymerizable carbon-carbon double bond, for example maleic anhydride and/or tetrahydrophthalic anhydride. In such condensation, for example polycondensation, it is possible, for example, first to prepare a linear or non-crosslinked condensation product, or a linear or non-crosslinked unsaturated polyester.

In addition to at least one dicarboxylic acid having at least one free-radically polymerizable carbon-carbon double bond and/or at least one dicarboxylic anhydride having at least one free-radically polymerizable carbon-carbon double bond, it is possible, in the preparation of condensation products or unsaturated polyester resins, to employ at least one dicarboxylic acid having no free-radically polymerizable carbon-carbon double bond, for example adipic acid and/or phthalic acid and/or isophthalic acid, and/or at least one dicarboxylic anhydride having no free-radically polymerizable carbon-carbon double bond, for example phthalic anhydride.

Since aromatic carbon-carbon bonds are not free radically polymerizable, polyesters or polyester resins containing only aromatic carbon-carbon bonds, such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), are not included in unsaturated polyesters or unsaturated polyester resins.

Furthermore, the unsaturated polyester resin may comprise, in particular, at least one monomer having at least one free-radically polymerizable carbon-carbon double bond, such as styrene and/or methyl methacrylate and/or diallyl phthalate, which may be copolymerized, in particular, with the condensation products or the unsaturated polyester.

Furthermore, the unsaturated polyester resin may for example comprise at least one initiator, in particular a peroxide initiator, such as dibenzoyl peroxide and/or methyl ethyl ketone peroxide.

Thus, the unsaturated polyester resin may comprise, for example, a particularly linear or non-crosslinked condensation product of at least one diol with at least one dicarboxylic acid having at least one free-radically polymerizable carbon-carbon double bond and/or with at least one dicarboxylic anhydride having at least one free-radically polymerizable carbon-carbon double bond, or a particularly linear or non-crosslinked unsaturated polyester having at least one free-radically polymerizable carbon-carbon double bond, at least one monomer having at least one free-radically polymerizable carbon-carbon double bond and at least one initiator. In this case, the condensation products or the unsaturated polyester resins can be crosslinked and the unsaturated polyester resins can be cured to thermoset plastics by, in particular, free-radical polymerization, for example copolymerization, of the condensates or unsaturated polyesters with at least one free-radically polymerizable carbon-carbon double bond and at least one monomer having at least one free-radically polymerizable carbon-carbon double bond.

Optionally, the unsaturated polyester resin may further comprise at least one accelerator and/or at least one inhibitor.

Unsaturated polyester resins have proven to be particularly advantageous since they have at least one repeating unit with at least one unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond which can react with at least one functional group of the mixed layer to form a covalent bond.

In this case, the at least one functional group of the hybrid layer can comprise or be an unsaturated functional group, in particular having at least one free-radically polymerizable carbon-carbon double bond, such as a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of a vinyl group, in particular singly or individually, and/or in the form of a vinyl group, for example an allyl group, which is bonded to a bridging group, and/or a vinylidene group.

The covalent bond can thus advantageously be formed by a free-radical addition reaction of at least one unsaturated functional group with at least one free-radically polymerizable carbon-carbon double bond of the unsaturated polyester and/or of at least one monomer of the unsaturated polyester resin with at least one unsaturated functional group of the mixed layer, in particular with at least one free-radically polymerizable carbon-carbon double bond.

In the context of a further alternative or additional embodiment of this embodiment, the resin, in particular the resin having at least one repeating unit with at least one functional group, comprises or is an epoxy resin (EP resin).

Epoxy resins are understood to mean, in particular, artificial resins or synthetic resins which comprise at least one monomer or prepolymer having epoxide groups, in particular having more than one epoxide group.

Here, the at least one prepolymer having epoxide groups may be, for example, a polyether having at least two terminal epoxide groups, for example a bisphenol diglycidyl ether, for example a bisphenol a diglycidyl ether, for example produced or obtained by reacting at least one bisphenol with epichlorohydrin and/or by a novolac having epoxide groups, for example in the form of glycidyl groups, for example produced or obtained by reacting at least one phenol with formaldehyde and by subsequent reaction with epichlorohydrin.

Furthermore, the epoxy resin may comprise in particular at least one hardener, for example at least one amine hardener, for example 1, 3-diaminobenzene and/or diethylenetriamine and/or 4,4' -methylenebis (cyclohexylamine), and/or at least one acidic hardener, for example at least one dicarboxylic acid anhydride such as hexahydrophthalic anhydride.

Thus, the epoxy resin may, for example, comprise at least one monomer or prepolymer having epoxy groups and at least one hardener. In this case, the epoxy groups can crosslink in an addition reaction with the functional groups of the at least one hardener and harden to a thermoset.

Optionally, the epoxy resin may also include at least one accelerator and/or at least one inhibitor.

Epoxy resins have proven to be particularly advantageous since they have at least one repeating unit with an epoxy group as a functional group which can react with at least one functional group of the mixed layer to form a covalent bond.

Advantageously, the epoxide group may react with an amine group and/or a hydroxyl group and/or a thiol group and/or a carboxylic acid group and/or an epoxide group to form a covalent bond.

Here, the at least one functional group of the hybrid layer may thus in particular comprise or be an amine group and/or a hydroxyl group and/or a thiol group and/or a carboxylic acid group and/or an epoxy group. Thus, a covalent bond can be formed by, in particular, an addition reaction of at least one epoxy group of the epoxy resin with an amine group and/or a hydroxyl group and/or a thiol group and/or a carboxylic acid group and/or an epoxy group of the hybrid layer.

Furthermore, in the case of epoxy resins, the at least one hardener may react with the at least one functional group of the mixed layer to form a covalent bond.

In the case of amine hardeners, the at least one functional group of the mixed layer may for this purpose contain, for example, epoxide groups and/or carboxylic acid groups.

In the case of acid hardeners, at least one functional group of the mixed layer can for this purpose, for example, comprise epoxy and/or amine groups and/or hydroxyl and/or thiol groups.

Thus, additional covalent bonds may advantageously be formed by reaction of the hardener of the epoxy resin with such functional groups of the hybrid layer.

In the context of a further alternative or additional embodiment of this embodiment, the resin, in particular the resin having at least one repeating unit with at least one functional group, comprises or is a vinyl ester resin (VE resin).

A vinyl ester resin is understood to mean, in particular, an artificial or synthetic resin which comprises at least one vinyl ester having at least one free-radically polymerizable carbon-carbon double bond.

The at least one vinyl ester may be prepared or obtained in particular by reaction, for example esterification, of at least one epoxy resin with methacrylic acid and/or acrylic acid. For example, in this reaction, for example in an esterification reaction, in particular uncrosslinked prepolymers can first be prepared.

In addition, the vinyl ester resin may comprise, in particular, at least one monomer having at least one free-radically polymerizable carbon-carbon double bond, for example styrene and/or methyl methacrylate and/or diallyl phthalate.

Furthermore, the vinyl ester resin may comprise, inter alia, at least one initiator, in particular a peroxide initiator, for example dibenzoyl peroxide and/or methyl ethyl ketone peroxide.

Thus, for example, the vinyl ester resin may comprise at least one vinyl ester having at least one free-radically polymerizable carbon-carbon double bond, at least one monomer having at least one free-radically polymerizable carbon-carbon double bond, and at least one initiator. In this case, for example, at least one vinyl ester is crosslinked by, in particular, free-radical polymerization, for example copolymerization, between at least one vinyl ester having at least one free-radically polymerizable carbon-carbon double bond and at least one monomer having at least one free-radically polymerizable carbon-carbon double bond, and the vinyl ester resin is cured to give a thermoset.

In the case of novolak vinyl esters, for example, it is also possible to use at least one diisocyanate. It may allow additional crosslinking between the hydroxyl groups of the prepolymer to form polyurethane groups. Such vinyl ester resins may also be referred to as vinyl ester polyurethane resins (VEU resins) and may advantageously have a particularly high heat resistance.

Optionally, the vinyl ester resin may further comprise at least one accelerator and/or at least one inhibitor.

Vinyl ester resins have proven to be particularly advantageous since they have at least one repeating unit which has at least one unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond which can react with at least one functional group of the hybrid layer to form a covalent bond.

In this case, the at least one functional group of the hybrid layer can comprise or be, in particular, an unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond, such as a methacrylate group and/or an acrylate group and/or a vinyl group, for example in the form of a vinyl group, in particular singly or individually, and/or in the form of a vinyl group, for example an allyl group, which is bonded to a bridging group, and/or a vinylidene group.

Covalent bonds can thus be formed by a free-radical addition reaction of at least one unsaturated functional group with at least one free-radically polymerizable carbon-carbon double bond of the vinyl ester and/or at least one monomer of the vinyl ester resin with at least one unsaturated functional group of the hybrid layer, in particular with at least one free-radically polymerizable carbon-carbon double bond.

In addition, the vinyl ester resin may have at least one repeating unit with at least one hydroxyl group that can react with at least one functional group of the hybrid layer to form a covalent bond.

To this end, the at least one functional group of the hybrid layer may for example comprise an epoxy group and/or a carboxylic acid group and/or an amino group and/or a hydroxyl group and/or a thiol group.

Additional covalent bonds can thus advantageously be formed by addition reactions or esterification reactions or condensation reactions of the hydroxyl groups of the vinyl ester with the epoxy groups and/or carboxylic acid groups and/or amino groups and/or hydroxyl groups and/or thiol groups of the hybrid layer.

In particular, in method step c) the resin formulation is cured to a thermosetting plastic, which can be induced thermally and/or by radiation and/or by mixing two or more components, for example.

Within the scope of a further embodiment, in method step b), the resin formulation is produced by injection molding and/or by transfer molding (english: transfermolding) and/or by pressing and/or by lamination and/or by casting. For example, in method step b), at least the region of the component coated with the mixed layer can be encapsulated with a resin.

Within the scope of a further embodiment, the resin formulation used, in particular, in method step b) comprises at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive. For example, the resin used in particular in process step b) may comprise at least one so-called low-profile additive (LPA). A low-profile additive is to be understood in particular as a pulverulent additive which swells particularly strongly, for example at elevated temperatures, with particularly reactive diluents such as styrene and/or diallyl phthalate, and can thus compensate or even overcompensate for the (reaction) shrinkage of the substance, in particular of the resin formulation. For example, the at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive or the at least one low-profile additive may comprise or be polyethylene and/or polymethyl methacrylate (PMMA) and/or polystyrene and/or polyvinyl acetate. By adding at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive, for example at least one low-profile additive, the (reaction) shrinkage of the resin formulation during curing to a thermoset can advantageously be reduced, for example to zero, if desired optionally modified to a negative shrinkage, i.e. a volume increase. By reducing the shrinkage, in particular to zero, it is possible to reduce the stresses, for example mechanical and/or thermal stresses, in the component-plastic composite, which are particularly pronounced in the long-term adhesion, long-term impermeability and long-term stability of the composite. The addition of additives which at least reduce shrinkage, in particular inhibit shrinkage, such as low profile additives, can be particularly advantageous, in particular in the case of unsaturated polyester resins and/or vinyl ester resins.

Within the scope of a further alternative or additional embodiment, the resin formulation used in particular in process step b) also comprises at least one filler, for example at least one spherical filler, for example chalk and/or aluminum oxide and/or aluminum hydroxide, and/or at least one fibrous filler, for example reinforcing fibers, for example glass fibers, such as for example made of E, S and/or R glass, and/or quartz fibers and/or aluminum oxide fibers and/or carbon fibers and/or aramid fibers, and/or at least one platelet filler. By means of the type and/or amount of the at least one filler, the coefficient of thermal expansion of the resin formulation and/or the thermosetting plastic can advantageously be brought as close as possible to that of the component, for example. In this way, stresses in the component-plastic composite due to temperature changes can be advantageously reduced or avoided, and the temperature stability of the component-plastic composite can be increased, and the adhesion durability, impermeability and stability can be increased. It is thus advantageously possible to produce component-plastic composites which are sealed against liquid and gaseous media, such as liquids and corrosive gases, even after more than 1000, for example even after more than 2000, temperature changes and which also show no signs of corrosion. This may be particularly advantageous in the case of metal components, such as printed circuit boards. Furthermore, the mechanical properties of the thermoset and of the component-plastic composite can be specifically adjusted and/or the mechanical stability of the thermoset and of the component-plastic composite can be increased by means of at least one filler, in particular at least one fibrous filler. Furthermore, the thermal conductivity of the thermosetting plastic and of the component-plastic composite can be specifically adjusted and/or increased by the at least one filler. This is advantageous in particular in the case of large-volume shapes of thermosetting plastics and/or for dissipating heat from components, for example electronic and/or electrical components.

The resin formulation used in particular in process step b) may in particular comprise at least one fibrous filler. Fibrous fillers can advantageously significantly reduce the coefficient of thermal expansion and can also improve strength compared to other shaped fillers (e.g., spherical and/or platelet fillers).

In particular, the resin formulation used in particular in process step b) may be a so-called BMC substance (BMC; english: bulk Molding Compound (Bulk Molding Compound)). For example, the resin formulation used in particular in process step b) may comprise, for example, a resin in dough form mixed with at least one, in particular reactive, diluent, for example styrene and/or diallyl phthalate. The dough-like mixture can also comprise at least one fibrous filler and/or optionally at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive or at least one low-profile additive. The at least one, in particular reactive, diluent, for example styrene and/or diallyl phthalate, can also be used here for swelling the at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive or low-profile additive.

For example, the resin formulation used in particular in process step b) may comprise a total of from 10 to 30% by weight of a resin, for example an unsaturated polyester resin and/or vinyl ester resin and/or epoxy resin, in particular an unsaturated polyester resin and/or vinyl ester resin, optionally including shrinkage-reducing, in particular shrinkage-inhibiting, additives or low-profile additives, and a total of from 10 to 40% by weight of a fibrous filler, for example glass fibers. The resin formulation used in particular in process step b) may additionally contain a total of from 10 to 80% by weight of spherical and/or platelet-shaped fillers.

Within the scope of a further alternative or additional embodiment, the resin formulation used, in particular in method step b), also comprises at least one flame-retardant and/or flame-inhibiting additive. For example, the resin used in particular in process step b) may comprise aluminium hydroxide (ATH). The flammability of the thermosetting plastics can advantageously be reduced by at least one flame-retardant and/or flame-inhibiting additive, for example aluminum hydroxide (ATH), for example from fire class HB to fire class V0. This in turn can improve the safety of the component-plastic composite.

Within the scope of a further embodiment, the component has a metal surface and/or the component is a metal component having a metal surface. In this case, in particular in method step a), the metal surface of the component can be coated, for example, partially or completely, with a partially inorganic and partially organic hybrid layer. In this way, the metal surface of the component can be protected from corrosion by the mixed layer and by the thermosetting plastic. Furthermore, the mixed layer can have a particularly high adhesion to the metal surface, which makes it possible to form a particularly stable component-plastic composite.

For example, the component can have a metal surface made of copper and/or a copper alloy and/or aluminum and/or an aluminum alloy and/or silver and/or a silver alloy, in particular copper and/or a copper alloy and/or silver and/or a silver alloy, for example copper. For example, the component can be a metal component made of copper and/or a copper alloy and/or aluminum and/or an aluminum alloy and/or silver and/or a silver alloy, in particular copper and/or a copper alloy and/or silver and/or a silver alloy, for example copper.

The metal surface of the component, in particular the metal surface which is coated, for example, partially or completely, with the partially inorganic and partially organic hybrid layer, in particular in method step a), can thus be made, for example, of copper and/or a copper alloy and/or silver and/or a silver alloy and/or aluminum and/or an aluminum alloy, in particular copper and/or a copper alloy and/or silver and/or a silver alloy, for example copper and/or a copper alloy.

The component can also advantageously be designed to be uneven. For example, the member may have a complex structure and/or complex geometry. For example, the metal surface of the component, in particular the metal surface which is coated in particular in method step a), for example partially or completely with a partially inorganic and partially organic hybrid layer, can be designed to be uneven, for example in the form of or complex in structure and/or geometry.

In particular, the component may have at least one curved surface that is at least partially concave, and/or at least one surface with at least one concave edge and/or at least one concave angle.

Within the scope of a further embodiment, the component comprises or is an electronic and/or electrical element.

For example, the component can be a sensor, for example a current sensor and/or a battery sensor, or a component of a sensor, for example a shunt for a sensor, for example a current sensor and/or a battery sensor, for example made of copper and/or a resistive alloy, for example a resistive material, and/or an electronic circuit, for example comprising a silicon chip and/or a Low Temperature co-fired ceramic (LTCC) and/or a printed circuit board, for example a printed circuit board provided with electronics, and/or an in particular electronic controller, and/or a flux concentrator and/or in particular an electrical conductor, for example a phase connector and/or a phase tap.

The component-plastic composite can be, for example, a sensor package and/or an encapsulated and/or encapsulated electronic circuit, for example, an electronic circuit comprising a silicon chip and/or a Low Temperature Cofired Ceramic (LTCC) and/or a printed circuit board, for example, a printed circuit board provided with electronics, and/or a lead through which an electrical conductor passes, in particular, through a thermosetting plastic.

In particular, the method can be designed for producing the component-plastic composite body according to the invention explained below.

With regard to further features and advantages of the method according to the invention, explicit reference is made here to the description of the component-plastic composite according to the invention in conjunction with the accompanying drawings, the description of the drawings and the examples.

The invention further relates to a component-plastic composite comprising a component. The component is at least partially coated with a partially inorganic and partially organic hybrid layer. Here a thermosetting plastic is applied to the mixed layer.

The partially inorganic and partially organic hybrid layer can advantageously have good adhesion properties to the resins used to form the thermoset and to the thermoset and can be both particularly tight, for example waterproof, and also particularly moisture-proof, if appropriate even gas-tight, and also particularly resistant to hydrolysis. The component can therefore advantageously already be protected, in particular also for a long time, from environmental influences, for example water, in particular also moisture, and possibly also gases, by the partially inorganic and partially organic hybrid layer, and/or such substances can be encapsulated in the component.

By means of the thermoset, the component can advantageously be better protected, in particular also over a long period of time, from environmental influences, such as water, in particular also moisture, and possibly also gases, and/or such substances can be better enclosed in the component. Furthermore, the components and the mixed layer can be protected from mechanical influences by the thermosetting plastic.

By means of the mixed layer and the thermosetting plastic, the component can advantageously be packaged in a sealed manner. The component-plastic composite can thus be designed, for example, as a sealed packaging.

Overall, the component-plastic composite can therefore advantageously be sealed, in particular also for a long time, for example waterproof and/or moisture-proof and/or gas-tight, and stable.

The mixed layer can be, in particular, a partially inorganic and a partially organic mixed layer containing silicon and oxygen.

Within the scope of a further embodiment, the hybrid layer comprises siloxane structures and/or amorphous silicon dioxide, for example siloxane structures and/or silsesquioxane structures and/or amorphous silicon dioxide. For example, the hybrid layer may be based on or optionally formed from a siloxane structure and/or an amorphous silica, such as a siloxane structure and/or a silsesquioxane structure and/or an amorphous silica. For example, the hybrid layer may comprise, e.g. be based on, optionally formed from, an organic-inorganic hybrid polymer having siloxane structures and/or silsesquioxane structures and/or amorphous silica domains. Such a mixed layer can advantageously have good adhesion properties to thermosetting plastics, is particularly compact, hydrolysis-resistant and stable, and also serves as an anti-corrosion layer for metal surfaces.

Within the scope of an embodiment, the hybrid layer is linked to the thermoset by covalent bonds. The covalent bond between the hybrid layer and the thermosetting plastic may be formed, inter alia, by reaction of at least one functional group of the hybrid layer with at least one functional group of at least one repeat unit of the resin forming the thermosetting plastic.

Since the hybrid layer is covalently bonded to the thermosetting plastic, a particularly strong bond of the thermosetting plastic to the hybrid layer can advantageously be achieved, which bond is much stronger than a purely physical bond. A particularly strong bond can thus be achieved between the component, the mixed layer and the thermosetting plastic.

Within the scope of a further embodiment, the thermoset is formed by curing of a resin formulation, in particular based on an unsaturated polyester resin and/or vinyl ester resin and/or epoxy resin.

Within the scope of a further embodiment, the hybrid layer is covalently bonded to the thermoset via alkyl units and/or amine units, for example secondary and/or tertiary amine units, and/or ether units and/or thioether units (R-S-R) and/or carboxylate units.

The covalent bonding of the mixed layer to the thermosetting plastic via the alkyl units can be formed, for example, by a radical reaction, in particular an addition reaction, of unsaturated functional groups, in particular having at least one free-radically polymerizable carbon-carbon double bond, for example methacrylate groups and/or acrylate groups and/or vinyl groups and/or allyl groups and/or vinylidene groups, on the mixed layer, with unsaturated functional groups, in particular having at least one free-radically polymerizable carbon-carbon double bond, for example methacrylate groups and/or acrylate groups and/or vinyl groups and/or allyl groups and/or vinylidene groups, on the thermosetting plastic or the resin used to form the thermosetting plastic.

The covalent bonding of the mixed layer to the thermosetting plastic through the amine unit may be formed, for example, by an addition reaction of an amino group on the mixed layer with an epoxy group on the thermosetting plastic or the resin for forming the thermosetting plastic, or conversely, by an addition reaction of an epoxy group on the mixed layer with an amino group on the thermosetting plastic or the resin for forming the thermosetting plastic.

Covalent attachment of the mixed layer to the thermosetting plastic via ether units can be formed, for example, by an addition reaction and/or condensation reaction of hydroxyl groups and/or epoxide groups on the mixed layer with epoxide groups and/or hydroxyl groups on the thermosetting plastic or the resin used to form the thermosetting plastic.

The covalent linkage of the mixed layer and the thermosetting plastic via the thioether unit may be formed, for example, by an addition reaction of a thiol group on the mixed layer and an epoxy group on the thermosetting plastic or the resin for forming the thermosetting plastic, or conversely, by an addition reaction of an epoxy group on the mixed layer and a thiol group on the thermosetting plastic or the resin for forming the thermosetting plastic.

The covalent linkage of the hybrid layer to the thermosetting plastic via the carboxylate unit can be formed, for example, by an addition reaction and/or esterification reaction of carboxylic acid groups on the hybrid layer with epoxide groups and/or hydroxyl groups on the thermosetting plastic or resin for forming the thermosetting plastic, or conversely, by an addition reaction and/or esterification reaction of epoxide groups and/or hydroxyl groups on the hybrid layer with carboxylic acid groups on the thermosetting plastic or resin for forming the thermosetting plastic.

Within the scope of a further embodiment, the organic portion of the mixed layer increases from the component toward the thermoset. In this case, for example, the concentration of at least one functional group and/or at least one further functional group and/or their decomposition products can increase from the component toward the thermoset. In this way, the advantageous properties of the hybrid layer can be further improved, in particular with regard to adhesion promotion and corrosion protection and/or impermeability.

For example, the mixed layer may have an average layer thickness in the range of 0.15.

Within the scope of a further embodiment, the component has a metal surface and/or the component is a metal component having a metal surface. In particular, the metal surface of the component can be partially or completely coated with a partially inorganic and partially organic hybrid layer.

The metal surfaces of the component, in particular the metal surfaces which are coated, for example, partially or completely, with the partially inorganic and partially organic hybrid layer, in particular in method step a), can thus be made, for example, of copper and/or a copper alloy and/or silver and/or a silver alloy and/or aluminum and/or an aluminum alloy, in particular copper and/or a copper alloy and/or silver and/or a silver alloy, for example copper and/or a copper alloy.

The component can also advantageously be designed to be uneven. For example, the member may have a complex structure and/or a complex geometry. For example, the metal surface of the component, in particular the metal surface which is coated in particular in method step a), for example partially or completely with a partially inorganic and partially organic hybrid layer, can be designed to be uneven, for example in the form of or complex structures and/or complex geometries.

Within the scope of a further embodiment, the component comprises or is an electronic and/or electrical element. The component can be, for example, a sensor, for example a current sensor and/or a battery sensor, or a component of a sensor, for example a shunt for a sensor, for example a current sensor and/or a battery sensor, for example made of copper and/or a resistive alloy, for example Resistan, and/or an electronic circuit, for example comprising a silicon chip and/or a Low Temperature Cofired Ceramic (LTCC) and/or a printed circuit board, for example a printed circuit board provided with electronics, and/or an in particular electronic controller, and/or a flux concentrator and/or in particular an electrical conductor, for example a phase connector and/or a phase tap.

The component-plastic composite body can be, for example, a sensor package and/or an encapsulated and/or encapsulated electronic circuit, for example an electronic circuit comprising a silicon chip and/or a Low Temperature Cofired Ceramic (LTCC) and/or a printed circuit board, for example a printed circuit board provided with electronics, and/or a lead through which a conductor, in particular an electrical conductor, passes through a thermosetting plastic.

Within the scope of a further embodiment, the thermoset comprises at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive and/or at least one filler and/or at least one flame-retardant and/or flame-inhibiting additive.

Within the scope of a further embodiment, the component-plastic composite is produced by the method according to the invention.

The component/plastic composite can be, for example, an injection molded or injection molded plastic/component composite. In this case, at least in the region of the mixed layer, the component can be overmolded and/or injection-molded with a thermosetting plastic or a resin formulation from which the thermosetting plastic is formed by curing.

The component-plastic composite can be, for example, a sealed packaging, in which, for example, the component is packaged in a sealed, in particular liquid-tight, for example waterproof and/or moisture-tight and/or gas-tight, in particular medium-tight manner, by means of the mixed layer and the thermosetting plastic applied thereto.

The component-plastic composites according to the invention and the component-plastic composites produced according to the invention can be characterized and/or detected by infrared reflectance spectroscopy (ATR) and/or interferometric reflectance methods. By means of infrared reflection spectroscopy, for example, the mixed layer can be characterized and detected here. For example, by means of infrared reflection spectroscopy, for example silicon compounds such as silanes and/or siloxanes and/or other silicon oxides and/or functional groups in thin layers on metal surfaces or plastic surfaces are detected, for example, in the form of characteristic fingerprints (english: Fingerprint). By means of the reflection spectrum, for example, the layer thickness can be determined.

With regard to further features and advantages of the component-plastic composite according to the invention, explicit reference is made here to the explanations and the drawings, the description and the examples of which taken in conjunction with the method according to the invention.

Drawings

Further advantages and advantageous designs of the subject matter according to the invention are shown by way of example in the figures and are explained in the following description. It should be noted herein that the drawings and examples are illustrative only and are not intended to limit the invention in any way.

Fig. 1 shows a schematic cross section of an embodiment of the component-plastic composite body according to the invention.

Detailed Description

Fig. 1 shows that the component-plastic composite 10 comprises a component 11. The component 11 is at least partially coated with a mixed layer 12, the mixed layer 12 being partly inorganic and partly organic, in particular containing silicon and oxygen. The hybrid layer 12 is coated with a thermosetting plastic 13.

The component 11 may in particular have a metallic surface, for example made of copper and/or silver and/or aluminum or alloys thereof. In this case, in particular the metal surface of the component 11 can be partially or completely coated with the mixed layer 12. The component 11 may comprise or be an electronic and/or electrical component, in particular.

Hybrid layer 12 can include or be formed from, for example, siloxane structures and/or silsesquioxane structures and/or amorphous silica, such as organic-inorganic hybrid polymers having siloxane structures and/or silsesquioxane structures and/or amorphous silica domains. The hybrid layer 12 can be formed, in particular, by means of a coating method from a gas phase comprising at least one organosilicon compound as a precursor, for example by chemical vapor deposition, the coating method comprising a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from one gas phase.

The thermosetting plastic 13 is formed by applying a resin formulation (for example, an unsaturated polyester resin and/or a vinyl ester resin and/or an epoxy resin) for forming the thermosetting plastic onto the mixed layer 12 and by curing the resin formulation.

The hybrid layer 12 may be covalently bonded to the thermoset 13 (not shown).

Examples

In a reactor, a series of tested previously cleaned components made of copper are each coated by Chemical Vapor Deposition (CVD; English: Chemical Vapor Deposition) at atmospheric pressure and at a temperature of 300 ℃ with a mixed layer which contains in particular silicon and oxygen and is partly inorganic and partly organic.

The layer was mixed by vapour deposition, the vapour phase here containing approximately 95% by volume of synthesis gas consisting of 95% by volume of nitrogen and 5% by volume of hydrogen, as well as acetic acid, water and tetramethyl orthosilicate as silicon-containing precursor, 3-aminopropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate. The total proportion of all silicon-containing precursors in the gas phase is between 0.5% and 1.0% (by volume), wherein tetramethyl orthosilicate makes up more than half of the total amount of silicon-containing precursors. 3-aminopropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate were present in the gas phase at a volume ratio of about 2: 1. Excess acetic acid was added based on the volume ratio of water to water, but not exceeding the 2:1 ratio.

An unsaturated polyester resin is coated onto the mixed layer to form a thermoset in the form of a frustoconical coupon, and cured to a thermoset.

For reference, to form a thermoset, an unsaturated polyester resin was applied as a frustoconical reference specimen to an uncoated, clean, homogeneous copper member and cured to form a thermoset.

In particular, some samples were subjected to a climate change test at a temperature varying between-30 ℃ and +160 ℃ and a relative air humidity varying between 10% and 95% over 6 days.

The adhesive strength of the test specimen and the reference specimen was then determined with and without prior climate change testing.

The test specimens which were not subjected to the climate change test showed almost twice the adhesive strength as the reference specimens which were not subjected to the climate change test.

And even after the climate change test, the test sample subjected to the climate change test still showed an adhesive strength higher by 30% or more than that of the reference sample not subjected to the climate change test.

The samples subjected to the climate change test showed no corrosion as did the samples not subjected to the climate change test.

The reference specimens subjected to the weathering test showed significant corrosion and adhesion failure during the weathering test.

Claims

1. A method for producing a component-plastic composite (10), comprising the following method steps:

a) coating the component (11) by means of a coating method, in particular a silicon-and oxygen-containing, partially inorganic and partially organic hybrid layer (12), which comprises a chemical reaction of at least one organosilicon compound as precursor and a deposition process from a gas phase;

b) applying a resin formulation for forming a thermoset (13) onto the hybrid layer (12); and

c) curing the resin formulation into the thermoset (13).

2. The process according to claim 1, wherein the coating in process step a) is carried out by chemical vapor deposition from a gas phase comprising at least one organosilicon compound as precursor.

3. The method according to claim 1 or 2,

wherein, in method step a), the gas phase comprises at least one organosilicon compound having at least one functional group as a precursor and a partially inorganic and partially organic hybrid layer (12) having at least one functional group is formed, and

wherein, in method step b), the resin formulation comprises a resin having at least one repeating unit with at least one functional group,

wherein a covalent bond is formed by reaction of at least one functional group of the hybrid layer (12) with at least one functional group of at least one repeating unit of the resin.

4. The process according to any one of claims 1 to 3, wherein the coating in process step a) is carried out at a temperature in the range of from 200 ℃ to 400 ℃, in particular from 250 to 350 ℃.

5. The process according to any one of claims 1 to 4, wherein the gas phase in process step a) is a reduced or inert gas phase, in particular wherein the gas phase comprises hydrogen.

6. Process according to any one of claims 1 to 5, wherein the gas phase in process step a) comprises at least one acid, in particular at least one Bronsted acid, and/or water, in particular wherein the gas phase in process step a) comprises at least one acid and water.

7. Method according to any one of claims 3 to 6, wherein at least one functional group of the hybrid layer (12) and/or of the at least one organosilicon compound comprises or is in particular an unsaturated functional group having at least one free-radically polymerizable carbon-carbon double bond and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiocarbamate group and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group and/or an isocyanate group and/or a thiocyanate group and/or an isothiocyanate group and/or a nitrile group.

8. The method according to any one of claims 3 to 7, wherein the at least one functional group of the hybrid layer (12) and/or of the at least one organosilicon compound comprises or is a methacrylate group and/or an acrylate group and/or a vinyl group and/or a vinylene group and/or an amino group and/or a hydroxyl group and/or a thiol group and/or a thiourethane group and/or a dithiourethane group and/or a carboxylic acid group and/or an epoxy group and/or a cyanate group and/or an isocyanate group and/or a thiocyanate group and/or an isothiocyanate group and/or a nitrile group.

9. A method according to any one of claims 1 to 8 wherein the at least one organosilicon compound comprises or is an organosilane.

10. The method according to any one of claims 3 to 9, wherein at least one functional group of the hybrid layer (12) and/or of the at least one organosilicon compound is bonded to silicon by a silicon-carbon bond.

11. The process according to any one of claims 3 to 10, wherein the gas phase in process step a) also comprises at least one further organosilicon compound having at least one further functional group as precursor.

12. The method of claim 11, wherein the first and second light sources are selected from the group consisting of,

wherein the at least one organosilicon compound having the at least one functional group comprises a methacrylate group and/or an acrylate group as functional groups, and

wherein the at least one further organosilicon compound having the at least one further functional group comprises amino groups and/or isocyanate groups as further functional groups, in particular wherein the mixed layer (12) comprises a reaction product from an addition reaction, in particular a michael addition, of amino groups with the methacrylate groups and/or acrylate groups.

13. The process according to any one of claims 1 to 12, wherein the gas phase in process step a) further comprises at least one silicate, in particular an orthosilicate.

14. Process according to any one of claims 1 to 13, wherein the gas phase in process step a) further comprises at least one non-functionalized organosilicon compound, in particular at least one silicate ester, wherein, preferably during process step a), the concentration of the at least one organosilicon compound having the at least one functional group and/or the concentration of the at least one further organosilicon compound having the at least one further functional group is increased and/or the concentration of the at least one non-functionalized organosilicon compound is reduced in the gas phase.

15. The method according to any one of claims 1 to 14, wherein the resin formulation comprises an unsaturated polyester resin and/or a vinyl ester resin and/or an epoxy resin, in particular an unsaturated polyester resin and/or a vinyl ester resin.

16. The method according to any one of claims 3 to 15, wherein at least one functional group of at least one repeating unit of the resin comprises or is an unsaturated functional group, and/or an epoxy group and/or a hydroxyl group, in particular having at least one free-radically polymerizable carbon-carbon double bond.

17. Process according to any one of claims 1 to 16, wherein, in process step b), the resin formulation is applied by injection moulding and/or by transfer moulding and/or by pressing and/or by lamination and/or by casting.

18. The method of any one of claims 1 to 17, wherein the resin formulation comprises:

-at least one shrinkage reducing additive; and/or

-at least one filler; and/or

-at least one flame retardant and/or flame retardant additive.

19. Method according to one of claims 1 to 18, wherein the component (11) has a metal surface, in particular made of copper and/or a copper alloy and/or silver and/or a silver alloy, and/or is a metallic component having a metal surface, in particular made of copper and/or a copper alloy and/or silver and/or a silver alloy, wherein in method step a) the metal surface of the component (11) is coated, for example partially or completely, with a partially inorganic and partially organic hybrid layer (12), in particular comprising silicon and oxygen, in particular wherein the metal surface of the component is designed in the form of an uneven, in particular complex structure and/or geometry.

20. The method according to any one of claims 1 to 19, wherein the member (11) comprises or is an electronic and/or electrical element.

21. A component-plastic composite (10) comprising a component (11),

wherein the component (11) is at least partially coated with a partially inorganic and partially organic mixed layer (12), in particular containing silicon and oxygen, and

wherein a thermosetting plastic material (13) is applied on the mixed layer (12).

22. The component-plastic composite (10) according to claim 21, wherein the hybrid layer (12) is connected to the thermosetting plastic (13) by a covalent bond.

23. The component-plastic composite (10) according to claim 21 or 22, wherein the thermosetting plastic (13) is formed by curing of a resin formulation based on unsaturated polyester resins and/or vinyl ester resins and/or epoxy resins.

24. The component-plastic composite (10) according to one of claims 21 to 23, wherein the mixed layer (12) is formed by

-alkyl units and/or

-amine units and/or

-ether units and/or

A thioether unit and/or

-a carboxylic acid ester unit,

covalently linked to said thermosetting plastic (13).

25. The component-plastic composite (10) according to one of claims 21 to 24, wherein the organic fraction of the hybrid layer (12) increases from the component (11) towards the thermoset (13).

26. The component-plastic composite (10) according to one of claims 21 to 25, wherein the mixed layer (12) comprises siloxane structures and/or silsesquioxane structures and/or amorphous silica, in particular organic-inorganic mixed polymers having siloxane structures and/or silsesquioxane structures and/or amorphous silica domains.

27. Component-plastic composite (10) according to one of claims 21 to 26, wherein the component (11) has a metal surface, in particular made of copper and/or a copper alloy and/or silver and/or a silver alloy, and/or is a metal component having a metal surface, in particular made of copper and/or a copper alloy and/or silver and/or a silver alloy, wherein the metal surface of the component (11) is partially or completely coated with a partially inorganic and partially organic, in particular silicon-and oxygen-containing, mixed layer (12), in particular wherein the metal surface of the component is designed in the form of an uneven, in particular complex, structure and/or geometry.

28. The component-plastic composite (10) according to any one of claims 21 to 27, wherein the component (11) comprises or is an electronic and/or electrical element.

29. The component-plastic composite (10) according to any one of claims 21 to 28, wherein the thermoset (13) comprises:

-at least one shrinkage reducing additive; and/or

-at least one filler; and/or

-at least one flame retardant and/or flame retardant additive.

30. The component-plastic composite (10) according to any one of claims 21 to 29, wherein the component-plastic composite (10) is manufactured by a method according to any one of claims 1 to 19.