EP4055203A1

EP4055203A1 - Process for producing a component-plastics bond

Info

Publication number: EP4055203A1
Application number: EP20803452.0A
Authority: EP
Inventors: Till Merkel; Jan Szabo; Philipp-Morris Egle; Gustav Klett; Martin Schuerer; Wilfried Aichele
Original assignee: Wieland Wicoatec GmbH; Robert Bosch GmbH
Current assignee: Wieland Wicoatec GmbH; Robert Bosch GmbH
Priority date: 2019-11-06
Filing date: 2020-11-02
Publication date: 2022-09-14
Also published as: DE102019217123A1; WO2021089466A1; CN114929932A

Abstract

The present invention relates to a process for producing a component-plastics bond (10). In order to cost-effectively provide a permanently impervious and stable component-plastics bond, in a process step a): a component (11) comprising a part-inorganic and part-organic hybrid layer (12) is coated using a coating method comprising a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase; in a process step b) a resin formulation is applied to the hybrid layer (12) in order to form a thermosetting plastic (13); and in a process step c) the resin formulation is cured to form the thermosetting plastic (13). The invention also relates to a component-plastics bond of this type.

Description

description

title

Process for the production of a component-plastic composite

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

State of the art

Electronic and electrical circuits are often encapsulated by casting and / or by transfer molding with thermosetting plastics, which can be formed, for example, by curing epoxy resins (EP).

However, epoxy resins are mostly produced via a condensation reaction of epichlorohydrin and as a result usually contain alkali metal chlorides, which promote the corrosion of metal surfaces. This is why epoxy resins are painstakingly cleaned for so-called first-level overmoulding, in which they are in direct contact with electrical and / or electronic circuits.

In what is known as second-level overmolding, electronic and / or electrical circuits 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 with the formation of oxides, which generally adhere poorly to the base metal. However, this affects the adhesion of paint layers, which is why by Coating with a layer of lacquer only delays the corrosion and formation of oxides on metal surfaces, but cannot be completely prevented. Metal surfaces coated with paint can corrode over time, which can lead to the formation of a gap and thus to a leak between the paint and the metal surface.

Some metals, such as copper, can be protected from corrosion by anti-corrosion layers made from corrosion inhibitors such as 1,2,3-benzotriazole, trotyltriazole or benzimidazole. However, as a rule, no thermosetting plastics adhere to such corrosion protection layers.

The documents JP 2002-003703, JP 2001-002894 and JP 627761 relate to compositions for sealing electronic elements.

Disclosure of the invention

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

The method comprises in particular a method step a) in which a component is coated with a partially inorganic and partially organic hybrid layer 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. The at least one organosilicon compound can in particular be designed as a precursor for forming the hybrid layer.

An organosilicon compound can in particular be understood as meaning a compound which has at least one, in particular direct, silicon-carbon bond (Si-C) and / or in which carbon, in particular indirectly, via at least one further element, for example via oxygen (Si-C) OC) or nitrogen (Si-NC) or sulfur (Si-SC), is bonded to silicon. Furthermore, the method comprises, in particular, a method step b) in which a resin formulation for forming a thermosetting plastic is applied to the hybrid layer. The resin formulation for forming a thermosetting plastic can in particular comprise or contain a resin for forming a thermosetting plastic. The at least one resin for forming a thermosetting plastic can be, for example, a synthetic resin or a synthetic resin.

A thermoset plastic can also be referred to as a thermoset or Duromer or Thermodur. A thermosetting plastic can in particular by curing a resin formulation, in particular a resin contained in a resin formulation, for example a synthetic resin or synthetic resin, in particular which is present before curing in the form of a meltable solid and / or a liquid or viscous and / or highly viscous material can be obtained or designed. The resin formulation and the thermosetting plastic formed therefrom can be filled or compounded with at least one filler or else unfilled or uncompounded, for example. After curing, the thermosetting plastic can in particular be resistant to deformation.

The resin formulation and / or the resin for forming a thermosetting plastic can be applied to the hybrid layer in process 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, in particular, a method step c) in which the resin formulation hardens or is hardened to form the thermoset plastic. In particular, the resin of the resin formulation can harden or be hardened.

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

The coating process, which involves a chemical reaction of at least one organosilicon compound as a precursor and one Comprising the deposition process from a gas phase, a particularly thin, partially inorganic and partially organic hybrid layer can advantageously be formed, which serve as an adhesion promoter, in particular between the component and the thermosetting plastic, have good adhesion properties for thermosetting plastics and are particularly dense, for example waterproof and in particular also moisture-tight and possibly even gas-tight, as well as particularly stable and, in particular, hydrolysis-resistant. Because the partially inorganic and partially organic hybrid layer formed in this way has a high resistance to hydrolysis, its adhesion properties, impermeability and stability can advantageously be maintained over the long term and the component can also be protected from corrosion.

The coating method according to the invention can also advantageously - for example in contrast to liquid-based coating methods, for example by means of a solution and / or dispersion and / or emulsion, which when coating complex structures and / or geometries due to capillary forces lead to the formation of uneven layers Components with uneven surfaces, for example with complex structures and / or with complex geometries, in particular components with uneven, in particular complex-structured and / or geometrically complex, metallic surfaces, in particular with at least one at least partially concavely curved surface and / or with at least one Surfaces with at least one concave edge and / or at least one concave corner, with a uniformly thin and dense, and in particular also uniformly stable and hydrolysis-resistant, in particular adhesion-promoting, partially inorganic u nd partially coated organic hybrid layer.

The coating process, which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, in particular in process step a), can in particular form a silicon- and oxygen-containing, partially inorganic and partially organic hybrid layer. For example, the coating process, which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, in particular in process step a), can be used to form a partially inorganic and partially organic hybrid layer comprising siloxane structures and / or amorphous silicon dioxide, for example, be based thereon, optionally be formed from it.

In particular, the coating method, which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, in particular in method step a), can be used to form a partially inorganic and partially organic hybrid layer which has siloxane structures and / or silsesquioxane structures and / or comprise amorphous silicon dioxide, for example based thereon, optionally be formed therefrom.

For example, by means of the coating process, which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, in particular in process step a), organic-inorganic hybrid polymers with siloxane structures and / or silsesquioxane structures and / or or areas of amorphous silica are formed.

A silsesquioxane can in particular be understood as meaning a siloxane with a cage-like and / or polymeric or oligomeric structure based on silicon-oxygen-silicon bridges (-Si-O-Si-) and tetrahedral silicon corner points. For example, silsesquioxanes can comprise, in particular be based on, a siloxane unit of the general chemical formula: - [SiO _1.5 X] _n -, where n stands for the number of these siloxane units and X stands for an organic radical, hydrogen, for example Halogen or another substituent which can be terminating or optionally also bridging and / or linking. Silsesquioxanes can be polymeric or oligomeric and / or cage-like. Polymeric silsesquioxanes can for example have a random and / or ladder-shaped and / or also cage-like basic structure. Cage-like silsesquioxanes can in particular have a cage-like basic structure composed of a plurality of siloxane units, for example of [SiO _1.5 R] units, per cage, for example of up to 18 siloxane units, for example of up to 18 [SiO _1.5 R] units per cage. In addition, cage-like silsesquioxanes can be oligomerically or polymerically linked to one another and thus be both cage-like and oligomeric or polymeric. Examples of cage-like silsesquioxanes are octasilsesquioxanes, which have a basic structure in the form of an octahedral cage made up of 8 siloxane units, for example 8 [SiO _1.5 R] units, and can also be linked oligomerically or polymerically, for example Polyoctahedral Silsesquioxane (POSS; English: Polyoctahedral

Silsesquioxanes). Further examples of cage-like silsesquioxanes are decasilsesquioxanes, which have a basic structure in the form of a cage of 10 siloxane units, for example 10 [SiO _1.5 R] units, and can also be linked oligomerically or polymerically.

Silicon-oxygen structural elements, for example siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide, can in particular represent an inorganic part of the hybrid layer.

Organic constituents and / or organic reaction products of the at least one organosilicon compound and / or organic groups on silicon atoms of silicon-oxygen structural elements formed from the at least one organosilicon compound, for example siloxane and / or silsesquioxane structures, can in particular form an organic part of the hybrid layer represent.

Because the partially inorganic and partially organic hybrid layer can be particularly tight, for example liquid-tight, for example waterproof, and in particular also moisture-tight and possibly even gas-tight, and stable and in particular also particularly hydrolysis-resistant, the component can advantageously, in particular long-term, against environmental influences such as water and especially moisture and possibly also from gases and other surrounding media as well as from corrosion and dust are protected and / or such substances are included in the component.

Since the hybrid layer already protects the component from environmental influences, 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.

Because the partially inorganic and partially organic hybrid layer has good adhesion properties for thermosetting plastics, good adhesion of the thermosetting plastic to the hybrid layer can advantageously be achieved.

Because the resin formulation is applied to the partially inorganic and partially organic hybrid layer and cured to form the thermosetting plastic, the component can then advantageously be even better, in particular permanently, against environmental influences such as water and in particular moisture and possibly also against gases and others Media and, for example, also be protected from dust and / or such substances are even better enclosed in the component. In addition, the component and the hybrid layer can be protected from mechanical influences by the thermoset plastic. By using thermosetting plastics, these advantages can also be maintained for significantly longer than when using other plastics, such as thermoplastics. This can be due, among other things, to the fact that when resin formulations cure to form thermoset plastics, significantly lower shrinkage can occur than, for example, when thermoplastics solidify, and that thermoset plastics can have a lower tendency to swell than other plastics, which reduces and / or prevents internal stresses and in this way permanent adhesion, tightness and stability of the plastic composite component can be achieved.

In addition, thermosetting plastics can be made from inexpensive materials. In addition, in the case of resin formulations with greater wall thicknesses for the formation of thermosetting plastics, they can be hardened faster than the solidification of thermoplastic melts. Both can in turn have an advantageous effect on the economy of the manufacturing process.

Due to the hybrid layer and the thermosetting plastic, the component can advantageously, in particular permanently, be packed tightly. The component-plastic composite can therefore, for example, be designed as a sealed packaging.

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

The partially inorganic and partially organic hybrid layer formed in process step a) can in particular contain silicon and oxygen. For example, the partially inorganic and partially organic hybrid layer formed in method step a) can comprise, for example be based on, or optionally be formed from siloxane structures and / or amorphous silicon dioxide, for example siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide . For example, the partially inorganic and partially organic hybrid layer formed in method step a) can comprise organic-inorganic hybrid polymers with siloxane structures and / or silsesquioxane structures and / or areas of amorphous silicon dioxide, for example based thereon, or optionally be formed therefrom.

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

In the context of one embodiment, the coating in process step a) therefore takes place by means of chemical vapor deposition, in particular from a gas phase, which comprises at least one organosilicon compound as a precursor, in particular for forming the hybrid layer. For example, in method step a), a component or the component can be coated with a partially inorganic and partially organic hybrid layer by means of chemical vapor deposition from a gas phase comprising at least one organosilicon compound as a precursor. The chemical vapor deposition can in particular be carried out at atmospheric pressure.

By chemical vapor deposition from a gas phase, which comprises at least one organosilicon compound as a precursor, an, in particular silicon and oxygen-containing, partly inorganic and partly organic hybrid layer, in particular which is particularly dense, for example waterproof and in particular also moisture-proof and possibly even can be gas-tight, as well as particularly hydrolysis-resistant and, for example, siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide, for example organic-inorganic hybrid polymers with siloxane structures and / or silsesquioxane structures and / or areas made of amorphous silicon dioxide and / or can be based thereon and / or be formed therefrom. In addition, by means of chemical vapor deposition, in which the reaction is activated without plasma, more uniform layers can advantageously be achieved than by plasma methods, in which, due to the effects of the electric field, disadvantageous elevations of the layer can occur at corners and edges.

Coating methods which include a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, such as, for example, a chemical gas phase deposition from a gas phase, which includes at least one organosilicon compound as a precursor, also advantageously make it possible, in particular also at high temperatures, for example from to 300 ° C, a partially inorganic and partially organic hybrid layer with at least one functional group, in particular using at least one organosilicon compound with at least one functional group as a precursor, in such a way that the at least one functional Group can still be retained on the partially inorganic and partially organic hybrid layer even after the coating process has been completed.

Up to now, this has not been possible using conventional coating processes.

In conventional coating processes, in which layers are formed by applying organosilanes from solution and dried at low temperatures, in particular only organic layers are formed which may be equipped with functional groups and initially have good adhesion properties, but due to the lack of an inorganic component , 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, and in the absence of sufficient crosslinking in itself and with a metal surface usually one have low resistance to hydrolysis and offer no protection against corrosion, which is why the initially good adhesion properties are usually lost under the action of moisture.

In other conventional coating processes, in which layers are formed by applying organosiloxane lacquers and baked in air, inorganic layers are formed which may be hydrolysis-resistant and offer corrosion protection, but usually poor adhesion properties due to the lack of an organic component, in particular a lack of functional groups have and are therefore also used as mold release agents in tools for plastic molding. During the baking process in air, functional groups are destroyed by oxidation, which is why layers produced in this way no longer have any functional groups after baking.

In the context of a further embodiment, a partially inorganic and partially organic hybrid layer with at least one functional group is therefore formed in method step a). For example, in method step a), one or the component with one or the partially inorganic and partially organic hybrid layer can also be used at least one functional group by means of a coating process which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, for example by means of chemical vapor deposition from a gas phase comprising at least one organosilicon compound as a precursor.

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 with at least one functional group as a precursor, in particular for forming the hybrid layer.

Because the partially inorganic and partially organic hybrid layer formed in process step a) is equipped with at least one functional group, it can advantageously be made possible that the at least one functional group of the hybrid layer react with at least one functional group of a resin of the resin formulation and a covalent bond can form between the hybrid layer and the thermoset plastic, in particular formed from the resin formulation. Compared to purely adhesive forces (physisorption), covalent bonds can be stronger by at least a factor of 10. In this way, a particularly strong and, in particular, hydrolysis-resistant connection of the thermosetting plastic to the hybrid layer can be achieved, in particular which can be significantly stronger than a purely physical adhesion. A particularly long-lasting, strong and dense bond between the component, the hybrid layer and the thermosetting plastic can thus be achieved.

In the context of a further embodiment, the resin formulation in process step b) therefore comprises a resin with at least one repeating unit with at least one, in particular covalently attached, functional group. In particular, a reaction of the at least one functional group of the hybrid layer with the at least one functional group of the at least one repeating unit of the resin can form a covalent bond, in particular between the hybrid layer and the thermosetting plastic, in particular formed from the resin.

In one embodiment, the coating in process step a) takes place at a temperature in a range from 200 ° C to 400 ° C. For example, the coating in process step a) can take place at a temperature in a range from 250 ° C to 350 ° C. This has proven to be particularly advantageous for the formation of a partially inorganic and partially organic hybrid layer, in particular with at least one functional group. Such coating temperatures can be comparatively low compared to the coating temperatures of other coating processes, for example for the formation of silicon dioxide layers. Such coating temperatures can advantageously be low enough to enable, for example, a coating of circuit boards already equipped with electronics. In method step a), such a coating temperature can be achieved, for example, by a so-called semi-hot wire method or by a so-called hot wall method.

In a further embodiment, the gas phase in process step a) is a reducing or inert gas phase. In particular, can the gas phase in process step a) be a reducing gas phase. For example, the gas phase in method step a) can comprise hydrogen, for example forming gas, for example nitrogen and / or argon and hydrogen. In this way, the at least one functional group of the hybrid layer or the at least one organosilicon compound can advantageously be protected from oxidation.

In a further embodiment, the gas phase in process step a) comprises at least one acid, in particular at least one Brønsted acid, for example at least one carboxylic acid, for example acetic acid, and / or water. The at least one acid, in particular Brønsted acid, for example carboxylic acid, can advantageously catalyze and / or accelerate chemical reactions of the at least one organosilicon compound in the gas phase during the coating process, for example during chemical vapor deposition. For example, through the at least one acid, in particular Brønsted acid, for example carboxylic acid, and / or through the water In one embodiment, the coating in process step a) takes place at a temperature in the range of

advantageously silicon-oxygen-carbon bonds (Si-OC) of organosilicon compounds in the gas phase during the coating process, for example in chemical vapor deposition, are partially hydrolyzed to silanols (Si-OH), which in turn can partially bond to the surface of the component and can partially condense with elimination of water, for example to form siloxanes (-Si-O-Si-) and / or structures made of silicon dioxide, in particular amorphous silicon dioxide. In the partially inorganic and partially organic hybrid layer that is formed in the process, oxygen can partially originate from the water contained in the gas phase. The water can also advantageously increase the dissociation and thus the catalytic properties of the at least one acid, in particular Brønsted acid, for example carboxylic acid.

In particular, the gas phase in process step a) can therefore comprise at least one acid, in particular at least one Brønsted acid, for example at least one carboxylic acid, for example acetic acid, and water. In this way, advantageously, in particular rapid, formation of the partially inorganic and partially organic hybrid layer can be achieved. The presence of at least one acid and water can in particular cause the formation of the inorganic component, 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, support the hybrid layer. This has proven particularly advantageous for coating components with uneven surfaces, for example with complex structures and / or with complex geometries, in particular components with uneven, in particular complex-structured and / or geometrically complex, metallic surfaces.

In a further embodiment, the at least one functional group of the hybrid layer and / or the at least one organosilicon compound comprises or is an unsaturated, functional group, in particular with 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 (-OC≡N) and / or an isocyanate group (-N = C = O) and / or a thiocyanate group (-SC≡N ) and / or an isothiocyanate group (-N = C = S) and / or a nitrile group (-C≡N). These functional groups can be advantageous for forming a covalent bond with a functional group of the resin.

A thiocarbamate group, which can also be referred to as a thiourethane group, can be understood in particular as a group in which a nitrogen atom is bonded to a carbon atom and the carbon atom is in turn bonded to at least one sulfur atom. The carbon atom is in particular still bound to an oxygen atom (-N-CS-O-) or to a further sulfur atom (-N-CS-S-).

In the context of a special configuration of this embodiment, the at least one functional group of the hybrid layer and / or 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 an, in particular simple, group or sole vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group and / or an amino group and / or a hydroxyl group and / or a thiol group and / or a thion urethane group and / or a thiol urethane 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 can be particularly advantageous for forming a covalent bond with a functional group of the resin.

An ethenylene group can be understood to mean, in particular, a bridging, substituted or unsubstituted ethene group. For example, an ethenylene group can be based on the general chemical formula: -CR = CR ^* -, where R and R ^{* can} each independently represent hydrogen or a substituent, in particular hydrogen. A thion urethane group can in particular be understood as meaning a thiocarbamate group in which the carbon atom is bonded to a sulfur atom via a double bond and to an oxygen atom via a single bond. For example, a thion urethane group can be based on the general chemical formula: -NR-CS-OR *, where R and R * can each independently represent hydrogen or a substituent, in particular hydrogen.

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

A dithiourethane group can in particular be understood as meaning a thiocarbamate group in which the carbon atom is bonded to a sulfur atom via a double bond and to a further sulfur atom via a single bond. For example, a dithiourethane group can be based on the general chemical formula: -NR-CS-S-R *, where R and R * can each independently represent hydrogen or a substituent, in particular hydrogen.

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

For example, the at least one functional group of the at least one organosilicon compound can be an unsaturated functional group, in particular with at least one 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 a, in particular simple or sole vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group, and / or an amino group and / or a hydroxyl group and / or a thiol group and / or a thiocarbamate group, for example a thion urethane group and / or a thiol urethane group and / or a dithiourethane group, and / or a carboxylic acid group and / or an epoxy group and / or comprise or be a cyanate group and / or an isocyanate group and / or a thiocyanate group and / or an isothiocyanate group and / or a nitrile group.

Unsaturated functional groups, in particular with 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 ethenylene groups, and / or Amino groups and / or hydroxyl groups and / or thiol groups and / or thiocarbamate groups, for example thion urethane groups and / or thiol urethane groups and / or dithiourethane groups, and / or carboxylic acid groups and / or epoxide Groups of organosilicon compounds can advantageously be comparatively stable as such and at least essentially remain as such during the coating in process step a). Thus, when using at least one organosilicon compound with at least one such functional group, the hybrid layer can also comprise at least one corresponding functional group.

Cyanate groups (-O-C≡N) of organosilicon compounds can decompose, for example, to hydroxyl groups during coating in process step a). Thus, when using at least one organosilicon compound with at least one cyanate group, the hybrid layer can comprise at least one hydroxyl group.

Isocyanate groups (-N = C = O) of organosilicon compounds can hydrolyze during coating in process step a), for example, to carbamic acids (-NH- COOH), which can then decompose to form amino groups. Thus, when using at least one organosilicon compound with at least one isocyanate group, the hybrid layer comprise at least one amino group.

Thiocyanate groups (-S-C N) of organosilicon compounds can decompose, for example, to thiol groups during coating in process step a). Thus, when using at least one organosilicon compound with at least one thiocyanate group, the hybrid layer can comprise at least one thiol group.

Isothiocyanate groups (-N = C = S) of organosilicon compounds can decompose during coating in process step a), for example, to thiocarbamate groups, for example thion urethane groups and / or thiol urethane groups. Thus, when using at least one

Organosilicon compound with at least one isothiocyanate group, the hybrid layer comprise at least one thiocarbamate group, for example thion urethane group and / or thiol urethane group.

Nitrile groups (-C N) of organosilicon compounds can differ

Coating in process step a) decompose, for example, into carboxylic acid groups. Thus, when using at least one

Organosilicon compound with at least one nitrile group, the hybrid layer comprise at least one carboxylic acid group.

The at least one functional group of the hybrid layer can therefore, for example, be an unsaturated functional group, in particular with at least one 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 an, in particular simple or sole, vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group, and / or an amino group and / or a hydroxyl group and / or a thiol group and / or a thiocarbamate group, for example a thion urethane group and / or a thiol urethane group and / or a dithiourethane group, and / or a carboxylic acid group and / or comprise or be an epoxy group. Unsaturated, functional groups on the hybrid layer can advantageously enter into an, in particular radical, reaction, for example an addition reaction, with unsaturated, functional groups on the resin, and in this way form a covalent bond between the hybrid layer and the thermosetting plastic formed from the resin.

Amino groups and / or hydroxyl groups and / or thiol groups and / or carboxylic acid groups and / or epoxy groups on the hybrid layer can advantageously enter into an addition reaction with epoxy groups on the resin and in this way form a covalent bond between the hybrid layer and the thermosetting plastic formed from the resin.

Hydroxy groups on the hybrid layer or on the resin can also advantageously enter into an esterification reaction or a condensation reaction with carboxylic acid groups or amino groups and hydroxyl groups and / or thiol groups on the resin or on the hybrid layer, and in this way a covalent reaction Form a bond between the hybrid layer and the thermosetting plastic formed from the resin.

Thiocarbamate groups, for example thion urethane groups and / or thiol urethane groups and / or dithiourethane groups, on the hybrid layer can advantageously enter into a reaction with amine groups of the resin and in this way a covalent bond between the hybrid layer and the one from the Form resin-formed thermosetting plastic.

Amino groups can also advantageously accelerate the reaction in the gas phase and enable a higher rate of layer formation. Thus, the reaction time can advantageously be shortened or, with an undiminished reaction time, greater layer thicknesses can be achieved than in the absence of amino groups. In addition, amino groups built into the hybrid layer can increase the elasticity of the hybrid layer and thus its mechanical strength. Thiol groups can also form stable metal-sulfur bonds with certain metals such as copper and / or silver. As a result, the adhesion of the hybrid layer to a metallic surface, for example made of copper and / or silver, of the component can advantageously be increased. In addition, thiol groups can advantageously be synthetically modified afterwards and in this way the properties of the hybrid layer can be modified.

Carboxylic acid groups can also advantageously improve the corrosion resistance of metals.

Thiocarbamate groups can also form stable metal-sulfur bonds with certain metals, such as copper and / or silver. As a result, the adhesion of the hybrid layer to a metallic surface, for example made of copper and / or silver, of the component can advantageously be increased. In addition, thiocarbamate groups can advantageously achieve better crosslinking within the hybrid layer. In addition, thiocarbamate groups can advantageously be synthetically modified afterwards and in this way the properties of the hybrid layer can be modified.

In a further embodiment, the at least one organosilicon compound comprises an organosilane. In particular, the at least one organosilicon compound can be an organosilane.

An organosilane can be understood in particular as a compound which comprises at least one, in particular direct, silicon-carbon bond (Si-C).

In the context of a further embodiment, the at least one functional group of the hybrid layer and / or of the at least one organosilicon compound is bonded to silicon via a silicon-carbon bond (Si-C). In this way, a hydrolysis-resistant connection of the at least one functional group to the silicon and thus to the hybrid layer can advantageously be realized. This in turn can advantageously a hydrolysis-resistant connection of the thermosetting plastic to the hybrid layer can be realized. The at least one organosilicon compound with the at least one functional group can in particular be an organosilane.

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

The at least one organosilicon compound with the at least one functional group can, for example, at least one vinylsilane, such as

Triethoxyvinylsilane and / or trimethoxyvinylsilane and / or tris (2-methoxyethoxy) vinylsilane, and / or at least one allylsilane, such as allyltrimethoxysilane, and / or at least one methacrylic acid or acrylic acid ester silane, for example at least one methacrylic acid or acrylic acid alkyl ester silane, such as methacrylic acid trimethoxy silane, such as methacrylic acid-3propethoxy silane-3propethoxy-silane and / or (3-acryloxypropyl) 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- (trimethoxysilyl) 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, such as 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 3-

Isocyanatopropyltrimethoxysilane, and / or at least one thiocyanatosilane, for example at least one thiocyanatoalkylsilane, such as 3-

Thiocyanatopropyltriethoxysilane, and / or at least one cyanosilane, for example at least one cyanoalkylsilane, such as (3-

Cyanopropyl) dimethylchlorosilane. In the context of a special configuration of this embodiment, the at least one organosilicon compound with the 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-acryloxypropyl) trimethoxysilane. In particular, the at least one organosilicon compound with the at least one functional group can comprise or be triethoxyvinylsilane and / or trimethoxyvinylsilane and / or allyltrimethoxysilane and / or tris (2-methoxyethoxy) vinylsilane.

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

In the context of one configuration of this embodiment, the gas phase in method step a) furthermore comprises at least one further organosilicon compound with at least one further functional group as a precursor, in particular for forming the hybrid layer. The at least one further functional group can, for example, modify the properties of the hybrid layer and / or improve the coating process, for example accelerate it, and / or 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 can be or react with the formation of a covalent bond.

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 stability and / or impermeability and / or hydrolysis resistance of the hybrid layer 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 connection of the thermosetting plastic to the hybrid layer and / or the hydrolysis resistance of this connection can advantageously be further improved .

The at least one further organosilicon compound with the at least one further functional group can in particular also be an organosilane. The at least one further functional group can in particular be attached to silicon via a silicon-carbon bond (Si-C).

The at least one further functional group can, for example, in particular be an unsaturated, functional group, in particular with at least one 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 an, in particular simple or sole, vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group, and / or an amino group and / or a hydroxyl group and / or a thiol group and / or a thiocarbamate group, for example a thion urethane group and / or a thiol urethane 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 include or be.

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

In the context of a special configuration of this embodiment, the at least one organosilicon compound comprises the at least one functional group a methacrylate group and / or an acrylate group, in particular a methacrylate group, as a functional group. The at least one further organosilicon compound with the at least one further functional group comprises an amino group and / or an isocyanate group, for example an amino group, as a further functional group. The at least one organosilicon compound with the at least one functional group and the at least one further organosilicon compound with the at least one further functional group can in particular be in the form of an organosilane. This has proven to be particularly advantageous both with regard to the long-term impermeability and stability of the hybrid layer and also with regard to the long-term adhesion properties of the hybrid layer.

For example, the at least one organosilicon compound with the at least one functional group 3-trimethoxysilylpropyl methacrylate and / or (3-acryloxypropyl) trimethoxysilane and the at least one further organosilicon compound with the at least one further functional group (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.

In this case, the hybrid layer can in particular have a reaction product from an addition reaction, in particular a Michael addition, of one or the amino group to the methacrylate group and / or acrylate group. For example, the reaction product can be a propyl 4-aza-2-heptanoate group:

Furthermore, the gas phase in process step a) can, for example, also contain at least one unfunctionalized organosilicon compound, that is to say one Organosilicon compound having no functional group as a precursor. The at least one unfunctionalized organosilicon compound can be, for example, a symmetrical or asymmetrical, in particular symmetrical, silicic acid ester.

In a further, alternative or additional embodiment, the gas phase in process step a) furthermore comprises at least one, for example symmetrical or asymmetrical, in particular symmetrical, silicic acid ester. By using the at least one silicic acid ester, the silicon dioxide content of the hybrid layer can advantageously be increased. In this way, the properties of the hybrid layer can be set in a targeted manner.

In particular, the gas phase in process step a) can furthermore comprise at least one, for example symmetrical or asymmetrical, in particular symmetrical, orthosilicic acid ester.

In the context of one configuration of this embodiment, the at least one silicic acid ester, in particular orthosilicic acid ester, comprises or is at least one silicic acid ester, in particular orthosilicic acid ester, of the general chemical formula:

R10, R11, R12 and R13 can each independently represent an alkyl group, for example a methyl group or an ethyl group or a propyl group, for example an n-propyl group or an i-propyl group, or a butyl group, for example an n-butyl group or an i-butyl group or a t-butyl group.

For example, the at least one silicic acid ester, in particular ortho-silicic acid ester, may comprise or be tetraethylorthosilicate (TEOS) and / or tetrapropylyorthosilicate (TPOS) and / or tetramethylorthosilicate (TMOS). Through the The use of tetraethylorthosilicate (TEOS) and / or tetrapropylyorthosilicate (TPOS) can advantageously increase the process reliability compared to tetramethylorthosilicate.

In particular, the at least one silicic acid ester can comprise or be an ortho-silicic acid ester, in particular tetramethylorthosilicate (TMOS) and / or tetraethylorthosilicate (TEOS).

In a further embodiment, the gas phase in process step a) further comprises at least one unfunctionalized organosilicon compound, in particular at least one, for example symmetrical or asymmetrical, in particular symmetrical, silicic acid ester. In particular, the concentration of the at least one organosilicon compound with the at least one functional group and / or the concentration of the at least one further organosilicon compound with the at least one further functional group and / or the concentration of the at least one unfunctionalized organosilicon compound can be increased in the gas phase during process step a) be reduced.

Unfunctionalized organosilicon compounds, such as silicic acid esters, can advantageously bond particularly well to metallic surfaces, with no functional groups being required for this. In that during method step a) the concentration of the at least one organosilicon compound with the at least one functional group and / or the concentration of the at least one further organosilicon compound with the at least one further functional group and / or the concentration of the at least one unfunctionalized organosilicon compound is increased in the gas phase is reduced, the precursor (s) with the functional group (s) matched to the resin formulation is or are metered into the gas phase as the coating time progresses, so that the functional groups are mainly incorporated on the surface of the coating, which then later comes into contact with the resin formulation. In this way, the advantageous properties of the hybrid layer, in particular with regard to the promotion of adhesion as well as the corrosion protection and / or the tightness can be further improved.

In particular, the concentration of the at least one functional group and / or the at least one further functional group and / or their decomposition products from the component can increase in the direction of the surface of the hybrid layer to be coated with the resin formulation. In this way, partially inorganic and partially organic hybrid layers can advantageously be formed, in which the organic content increases in the direction from the component to the thermoset plastic. Such a gradient in the composition of the partially inorganic and partially organic hybrid layer can result from the process control described above in method step a) with concentrations of the precursors in the gas phase that have changed over time.

Before coating in process step a), the component can optionally be cleaned, for example degreased and / or pickled and / or washed, for example in a process step a0), and / or, for example in a forming gas atmosphere, dried and / or heat-treated.

In 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 can comprise or be an unsaturated polyester resin and / or a vinyl ester resin and / or an epoxy resin. Thermosetting plastics based on these resins can advantageously have a negligibly low swelling tendency, in particular under the influence of moisture and possibly also under the influence of other media. In this way, internal stresses caused by swelling, which could lead to a reduction in adhesion, tightness and stability, can be avoided. In addition, thermosetting plastics based on these resins can have high hydrolysis resistance and / or media resistance. This can be advantageous in particular with regard to the permanent adhesion, the permanent tightness and the permanent stability of the composite. Epoxy resins are also characterized by a low (reaction) shrinkage during curing to form the thermoset plastic.

In particular, the resin formulation can comprise an unsaturated polyester resin and / or a vinyl ester resin. For example, the resin can comprise or be an unsaturated polyester resin and / or a vinyl ester resin. In comparison to epoxy resins, unsaturated polyester resins and vinyl ester resins can contain significantly fewer or even hardly any or no production-related ionic impurities and / or can be significantly cheaper. The (reaction) shrinkage of resin formulations based on unsaturated polyester resins and vinyl ester resins can be higher than the resin formulations based on epoxy resins, but advantageously by adding shrinkage-reducing additives, so-called low-profile additives, down to zero and even up to less than zero.

For example, the resin formulation can comprise a vinyl ester resin. In particular, the resin can comprise or be a vinyl ester resin. Compared to polyester resins, vinyl ester resins can be more resistant to hydrolytic degradation.

In a further embodiment, the at least one functional group of the at least one repeating unit of the resin comprises or is 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 an ethenylene group, and / or an epoxy group and / or a hydroxyl group.

In the case of a resin with a repeating unit with an unsaturated, functional group, in particular with at least one radically polymerizable carbon-carbon double bond, the at least one functional group of the hybrid layer can in particular be an unsaturated functional group, in particular with at least one 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 an, in particular simple or sole, vinyl group and / or in the form of a bridging group attached vinyl group, for example allyl group, and / or an ethenylene group comprise or be.

By means of an, in particular radical, reaction, for example addition reaction, of the at least one unsaturated, functional group, in particular with at least one radically polymerizable carbon-carbon double bond, of the hybrid layer with the at least one unsaturated, functional group, in particular with at least one radically polymerizable carbon Carbon double bond, of the resin, alkylene units can be formed, via which a covalent bond can advantageously be formed between the hybrid layer and the thermosetting plastic formed from the resin.

In the case of a resin with a repeating unit with an epoxy group, the at least one functional group of the hybrid layer can in particular be an amino group and / or a hydroxyl group and / or a thiol group and / or a carboxylic acid group and / or a Epoxy group include or be.

An epoxy group can react with an amino group, for example, to form a secondary or tertiary amine unit bridging via a covalent bond. In particular, a hydroxyl group can be formed on a carbon atom which is adjacent to the carbon atom substituted with the amine group.

An epoxy group can react with a hydroxyl group, for example, in particular via an addition reaction, to form an ether unit bridging via a covalent bond. In particular, a hydroxyl group can be formed on a carbon atom which is adjacent to the carbon atom substituted with the ether group. An epoxide group can react with a thiol group, for example, in particular via an addition reaction, to form a thioether unit (RSR *) bridging via a covalent bond. In particular, a hydroxyl group can be formed on a carbon atom which is adjacent to the carbon atom substituted with the thioether unit.

An epoxy group can react with a carboxylic acid group, for example, in particular via an addition reaction, to form a carboxylic acid ester unit bridging via a covalent bond. In particular, a hydroxyl group can be formed on a carbon atom which is adjacent to the carbon atom substituted with the carboxylic acid ester unit.

An epoxy group can, for example, react with an epoxy group to form an ether unit bridging via a covalent bond or polymerize to form a polyether.

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

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

By a reaction, in particular an addition reaction or an esterification reaction or a condensation reaction, the hydroxyl group of the resin with the epoxy group and / or carboxylic acid group and / or thiol group of the hybrid layer can ether units or Carboxylic acid ester units are formed, via which a covalent bond can advantageously be formed between the hybrid layer and the thermosetting plastic formed from the resin.

In the context of a further embodiment, the resin with the at least one repeating unit with the 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 can advantageously have at least one repeating unit with at least one functional group which can react with the at least one functional group of the hybrid layer to form a covalent bond.

In the context of one configuration of this embodiment, the resin, in particular the resin with the at least one repeating unit with the at least one functional group, comprises or is an unsaturated polyester resin (UP resin).

An unsaturated polyester resin can in particular be understood as meaning a resin, in particular synthetic resin or synthetic resin, which is an, in particular oligomeric or polymeric, condensation product of at least one diol with at least one dicarboxylic acid with at least one free-radically polymerizable carbon-carbon double bond and / or with at least a dicarboxylic anhydride with at least one free-radically polymerizable carbon-carbon double bond. Such condensation products can also be referred to as unsaturated polyesters, in particular with at least one free-radically polymerizable carbon-carbon double bond.

The condensation product or the unsaturated polyester can in particular 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 with at least one 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 acid anhydride with at least one free-radically polymerizable carbon-carbon double bond, for example maleic anhydride and / or tetrahydrophthalic anhydride, are produced or obtainable. In this condensation, for example polycondensation, a linear or uncrosslinked condensation product or a linear or uncrosslinked unsaturated polyester can, for example, first be produced.

In addition to the at least one dicarboxylic acid with the at least one radically polymerizable carbon-carbon double bond and / or to the at least one dicarboxylic acid anhydride with the at least one radically polymerizable carbon-carbon double bond, in the production of the condensation product or the unsaturated polyester or the unsaturated polyester resin at least one dicarboxylic acid without a radically polymerizable carbon-carbon double bond, for example adipic acid and / or phthalic acid and / or isophthalic acid, and / or at least one dicarboxylic acid anhydride without a radically polymerizable carbon-carbon double bond, for example phthalic anhydride, can be used.

Since aromatic carbon-carbon bonds are not radically polymerizable, polyesters or polyester resins which only comprise aromatic carbon-carbon bonds, for example polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), are not unsaturated polyesters or respectively not counted among the unsaturated polyester resins.

Furthermore, an unsaturated polyester resin can in particular comprise at least one monomer with at least one free-radically polymerizable carbon-carbon double bond, for example styrene and / or methyl methacrylate and / or diallyl phthalate, in particular which can copolymerize with the condensation product or unsaturated polyester. In addition, an unsaturated polyester resin can, for example, comprise at least one initiator, in particular a peroxide initiator, for example dibenzoyl peroxide and / or methyl ethyl ketone peroxide.

An unsaturated polyester resin can thus, for example, be a, in particular linear or uncrosslinked, condensation product of at least one diol with at least one dicarboxylic acid with at least one radically polymerizable carbon-carbon double bond and / or with at least one dicarboxylic acid anhydride with at least one radically polymerizable carbon-carbon double bond or an, in particular linear or uncrosslinked, unsaturated polyester with at least one radically polymerizable carbon-carbon double bond, at least one monomer with at least one radically polymerizable carbon-carbon double bond and at least one initiator. The condensation product or the at least one monomer with the at least one free-radically polymerizable carbon-carbon double bond and the at least one monomer with the at least one free-radically polymerizable carbon-carbon double bond, respectively, of the condensation product or the unsaturated polyester with the at least one radically polymerizable carbon-carbon double bond and the at least one monomer the unsaturated polyester are crosslinked and the unsaturated polyester resin harden to form a thermosetting plastic.

Optionally, an unsaturated polyester resin can furthermore comprise at least one accelerator and / or at least one inhibitor.

Unsaturated polyester resins have proven to be particularly advantageous because they have at least one repeating unit with at least one unsaturated functional group with the at least one free-radically polymerizable carbon-carbon double bond, which can react with the at least one functional group of the hybrid layer to form a covalent bond . The at least one functional group of the hybrid layer can in particular be an unsaturated functional group, in particular with at least one radically polymerizable carbon-carbon double bond, for example a methacrylate group and / or an acrylate group and / or a vinyl group, for example in In the form of an, in particular simple or sole, vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group.

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

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

An epoxy resin can be understood in particular as a synthetic resin or a synthetic resin which comprises at least one monomer or prepolymer with epoxy groups, in particular with more than one epoxy group.

The at least one prepolymer with epoxy groups can, for example, be a polyether with at least two terminal epoxy groups, for example a bisphenol diglycidyl ether, for example a bisphenol A diglycidyl ether, for example produced or obtainable by reacting at least one bisphenol with epichlorohydrin, and / or a novolak with epoxy groups, for example in the form of glycidyl groups, for example produced or obtainable by reacting at least one Phenol with formaldehyde and subsequent reaction with epichlorohydrin.

Furthermore, an epoxy resin can 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 a dicarboxylic anhydride such as hexahydrophthalic anhydride.

An epoxy resin can thus comprise, for example, at least one monomer or prepolymer with epoxy groups and at least one hardener. The epoxy groups can be crosslinked in an addition reaction with functional groups of the at least one hardener and cure to form a thermoset plastic.

Optionally, an epoxy resin can furthermore comprise at least one accelerator and / or at least one inhibitor.

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

Epoxy groups can advantageously react with amine groups and / or hydroxyl groups and / or thiol groups and / or carboxylic acid groups and / or epoxy groups to form a covalent bond.

Thus, the at least one functional group of the hybrid layer can 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. A covalent bond can thus be achieved by a, in particular addition, reaction of the at least one epoxy group of the epoxy resin with the amine group and / or hydroxyl group and / or thiol group and / or carboxylic acid group and / or epoxy group of the hybrid layer be formed. In addition, in the case of epoxy resins, the at least one hardener can react with the at least one functional group of the hybrid layer to form a covalent bond.

In the case of an amine hardener, the at least one functional group of the hybrid layer can for this purpose comprise, for example, an epoxy group and / or a carboxylic acid group.

In the case of an acidic hardener, the at least one functional group of the hybrid layer can for this purpose comprise, for example, an epoxy group and / or an amine group and / or hydroxyl group and / or thiol group.

A reaction of the hardener of the epoxy resin with such a functional group of the hybrid layer can advantageously form an additional covalent bond.

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

A vinyl ester resin can in particular be understood as meaning a synthetic resin or a synthetic resin which comprises at least one vinyl ester with at least one free-radically polymerizable carbon-carbon double bond.

The at least one vinyl ester can in particular be produced or obtainable by reaction, for example esterification, of at least one epoxy resin with methacrylic acid and / or acrylic acid. In this reaction, for example esterification, an, in particular uncrosslinked, prepolymer can, for example, first be prepared. Furthermore, a vinyl ester resin can in particular comprise at least one monomer with at least one free-radically polymerizable carbon-carbon double bond, for example styrene and / or methyl methacrylate and / or diallyl phthalate.

In addition, a vinyl ester resin can in particular comprise at least one initiator, in particular a peroxide initiator, for example dibenzoyl peroxide and / or methyl ethyl ketone peroxide.

A vinyl ester resin can thus for example comprise at least one vinyl ester with at least one radically polymerizable carbon-carbon double bond, at least one monomer with at least one radically polymerizable carbon-carbon double bond and at least one initiator. In this case, by a, in particular radical, polymerization, for example copolymerization, between the at least one vinyl ester with the at least one radically polymerizable carbon-carbon double bond and the at least one monomer with the at least one radically polymerizable carbon-carbon double bond, for example the at least one vinyl ester are crosslinked and harden the vinyl ester resin to form a thermosetting plastic.

In the case of novolak vinyl esters, for example, at least one diisocyanate can also be used. This can enable additional crosslinking between hydroxyl groups of the prepolymer with the formation of urethane groups. Such vinyl ester resins can also be referred to as vinyl ester urethane resins (VEU resins) and can advantageously have a particularly high temperature resistance.

Optionally, a vinyl ester resin can furthermore comprise at least one accelerator and / or at least one inhibitor.

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

The 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 In the form of an, in particular simple or sole, vinyl group and / or in the form of a vinyl group attached to a bridging group, for example an allyl group, and / or an ethenylene group.

By a radical addition reaction of the at least one unsaturated, functional group with the at least one radically polymerizable carbon-carbon double bond of the vinyl ester and / or of the at least one monomer of the vinyl ester resin with the at least one unsaturated functional group, in particular with the at least one radically polymerizable carbon -Carbon double bond, the hybrid layer can form a covalent bond.

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

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

By means of an addition reaction or an esterification reaction or a condensation reaction of the hydroxyl group of the vinyl ester with the epoxy group and / or carboxylic acid group and / or amino group and / or hydroxyl group and / or thiol group of the hybrid layer, an additional covalent Bond are formed. The curing of the resin formulation to form the thermosetting plastic, in particular in process step c), can, for example, be thermally induced and / or radiation-induced and / or induced by mixing two or more components.

In a further embodiment, in process step b) the resin formulation is applied by injection molding and / or by transfer molding 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 hybrid layer can be coated with the resin.

In the context of a further embodiment, the resin formulation used in particular in process step b) comprises at least one shrinkage-reducing, in particular shrinkage-inhibiting,

Additive. For example, the resin used in particular in process step b) can comprise at least one so-called low-profile additive (LPA). A low-profile additive can in particular be understood to mean a powdery additive which, for example at an elevated temperature, swells, in particular strongly, with an, in particular reactive, thinner, for example styrene and / or diallyl phthalate, and thereby swells the (reaction) Can compensate for shrinkage of a mass, in particular resin formulation, or even overcompensate. 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, can advantageously reduce the (reaction) shrinkage of the resin formulation during curing to form the thermoset plastic, for example reduced to zero and, if desired, possibly down to a negative shrinkage, i.e. an increase in volume, to be modified. By reducing the shrinkage, in particular down to zero, tensions can be avoided For example mechanical and / or thermal stresses in which the component-plastic composite is reduced, which can have an advantageous effect, in particular with regard to the permanent adhesion, the permanent tightness and the permanent stability of the composite. An addition of at least shrinkage-reducing, in particular shrinkage-inhibiting,

Additive, for example low-profile additive, can be particularly advantageous in the case of unsaturated polyester resins and / or vinyl ester resins.

In the context of a further, alternative or additional embodiment, the resin formulation used in particular in process step b) furthermore comprises at least one filler, for example at least one spherical filler, for example chalk and / or aluminum oxide and / or aluminum trihydroxide, and / or at least one fibrous filler , for example reinforcing fibers, for example glass fibers, 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-shaped filler. The type and / or amount of the at least one filler can advantageously adapt the coefficient of thermal expansion of the resin formulation and / or of the thermosetting plastic, for example as closely as possible, to the coefficient of thermal expansion of the component. In this way, stresses in the component / plastic composite caused by temperature changes can advantageously be reduced or avoided and the temperature stability and thus the durability of the adhesion, tightness and stability of the component / plastic composite can be improved. In this way, component-plastic composites can advantageously be produced which are still tight against liquid and gaseous media, for example liquids and corrosive gases, and show no signs of corrosion even after more than 1000, for example even after more than 2000, temperature changes. This can be particularly advantageous in the case of metallic components such as circuit boards. In addition, the at least one filler, in particular the at least one fibrous filler, can specifically adapt the mechanical properties of the thermoset plastic and the component-plastic composite and / or the mechanical stability of the thermoset plastic and the component-plastic composite increase. In addition, the thermal conductivity of the thermosetting plastic and the component-plastic composite can be specifically adapted and / or increased by the at least one filler. This can be advantageous in particular in the case of voluminous shapes of the thermosetting plastic and / or for heat dissipation from the component, for example in the case of electronic and / or electrical components.

The resin formulation used in particular in process step b) can in particular comprise at least one fibrous filler. Fibrous fillers can advantageously reduce the coefficient of thermal expansion to a greater extent than the same proportions of fillers of different shapes, for example spherical and / or platelet-shaped fillers, and also increase the strength.

In particular, the resin formulation used, in particular in process step b), can be a so-called BMC compound (BMC; English: Bulk Molding Compound). For example, the resin formulation used in particular in process step b) can comprise the resin in a, for example dough-like, mixture with at least one, in particular reactive, thinner, for example styrene and / or diallyl phthalate. The, for example, dough-shaped, mixture can furthermore 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, thinner, for example styrene and / or diallyl phthalate, can additionally serve to swell 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),

10% by weight to 30% by weight in total of resins, for example unsaturated polyester resins and / or vinyl ester resins and / or epoxy resins, in particular unsaturated polyester resins and / or vinyl ester resins, optionally including shrinkage-reducing, in particular shrinkage-inhibiting additives or low-profile additives, and

10% by weight to 40% by weight in total of fibrous fillers, for example glass fibers. The resin formulation used, in particular, in process step b) can additionally comprise 10% by weight to 80% by weight in total of spherical fillers and / or platelet-shaped fillers.

In the context of a further, alternative or additional embodiment, the resin formulation used in particular in process step b) furthermore comprises at least one fire-retardant and / or flame-retardant additive. For example, the resin used in particular in process step b) can comprise aluminum trihydroxide (ATH). The at least one fire-retardant and / or flame-retardant additive, for example aluminum trihydroxide (ATH), can advantageously reduce the flammability of the thermosetting plastic, for example from fire class HB to fire class V0. In this way, the safety of the component-plastic composite can in turn be increased.

In the context of a further embodiment, the component has a metallic surface and / or the component is a metallic component with a metallic surface. In particular, in method step a), in particular the metallic surface of the component can be coated with the partially inorganic and partially organic hybrid layer, for example partially or completely. The metallic surface of the component can be protected from corrosion by the hybrid layer and the thermoset plastic. In addition, the hybrid layer can have a particularly high level of adhesion on metallic surfaces, which can enable the formation of a particularly stable component-plastic composite.

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

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

The component can advantageously also have an uneven design. For example, the component can have a complex structure and / or a complex geometry. For example, the metallic surface of the component, in particular which, in particular in method step a), is coated with the partially inorganic and partially organic hybrid layer, for example partially or completely, can be uneven, for example in the form of a complex structure and / or a complex geometry or complex structured and / or geometrically complex. In particular, the component can have at least one at least partially concavely curved surface and / or at least one surface with at least one concave edge and / or at least one concave corner.

In the context of a further embodiment, the component comprises or is an electronic and / or electrical component.

For example, the component can be a sensor, for example a current sensor and / or battery sensor, or a component of a sensor, for example a shunt, for example made of copper and / or a resistance alloy such as resist, for a sensor, for example a current sensor and / or Battery sensor, and / or an electronic circuit, for example which silicon chips and / or low-temperature cofired ceramics (LTCC; English: Low Temperature Cofired Ceramics) and / or a circuit board, for example a circuit board equipped with electronics, and / or a, in particular electronic, control device, and / or a flux concentrator and / or, in particular electrical, conductor, for example a phase connector and / or a phase tap.

The component-plastic composite can, for example, be a sensor encapsulation and / or an encased and / or encapsulated electronic circuit, for example which silicon chips and / or low-temperature fired ceramics (LTCC; English: Low Temperature Cofired Ceramics) and / or a printed circuit board, for example a printed circuit board equipped with electronics, and / or a leadthrough of an, in particular electrical, conductor through a thermosetting plastic.

In particular, the method can be designed to produce a component-plastic composite according to the invention which is explained later.

With regard to further technical features and advantages of the method according to the invention, explicit reference is hereby made to the explanations in connection with the component / plastic composite according to the invention and to the figure, the description of the figures and the exemplary embodiments.

In addition, the invention relates to a component-plastic composite which comprises a component. The component is at least partially coated with a partially inorganic and partially organic hybrid layer. A thermosetting plastic is applied to the hybrid layer.

The partially inorganic and partially organic hybrid layers can advantageously have good adhesion properties for resins for the formation of thermoset plastics and thermoset plastics and both particularly tight, for example waterproof and in particular also moisture-tight and possibly even gas-tight, as well as especially be resistant to hydrolysis. The component can thus advantageously already be protected by the partially inorganic and partially organic hybrid layers, in particular also in the long term, from environmental influences such as water and in particular also moisture and possibly also from gases and / or such substances can be enclosed in the component.

Due to the thermosetting plastic, the component can advantageously be protected even better, in particular also in the long term, from environmental influences such as water and in particular also moisture and possibly also from gases and / or such substances can be better enclosed in the component. In addition, the component and the hybrid layer can be protected from mechanical influences by the thermoset plastic.

The component can advantageously be packed tightly through the hybrid layer and the thermosetting plastic. The component-plastic composite can therefore be designed, for example, as a sealed packaging.

Overall, the component / plastic composite can thus advantageously be tight, for example waterproof and / or moisture-tight and / or gas-tight, and stable, in particular also in the long term.

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

In the context 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 can be based on siloxane structures and / or amorphous silicon dioxide, for example siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide, or optionally be formed therefrom. For example, the hybrid layer can comprise organic-inorganic hybrid polymers with siloxane structures and / or silsesquioxane structures and / or regions made of amorphous silicon dioxide, for example based thereon, optionally be formed therefrom. Such hybrid layers can advantageously have good adhesion properties Have thermoset plastic, be particularly dense, hydrolysis-resistant and stable and also serve as corrosion protection layers for metallic surfaces.

In one embodiment, the hybrid layer is connected to the thermosetting plastic via covalent bonds. The covalent bonds between the hybrid layer and the thermosetting plastic can in particular be formed by a reaction of at least one functional group of the hybrid layer with at least one functional group of at least one repeating unit of a resin forming the thermosetting plastic.

Because the hybrid layer is connected to the thermosetting plastic via the covalent bonds, a particularly strong connection of the thermosetting plastic to the hybrid layer can advantageously be achieved, which can be significantly stronger than a purely physical adhesion. A particularly strong bond between the component, the hybrid layer and the thermosetting plastic can thus be achieved.

In a further embodiment, the thermosetting plastic is formed by curing a resin formulation, in particular based on an unsaturated polyester resin and / or a vinyl ester resin and / or an epoxy resin.

In a further embodiment, the hybrid layer is via alkylene units and / or amine units, for example secondary and / or tertiary amine units, and / or ether units and / or thioether units (RSR *) and / or carboxylic acid ester Units covalently connected to the thermoset plastic.

A covalent connection of the hybrid layer with the thermosetting plastic via alkylene units can be achieved, for example, by a radical reaction, in particular an addition reaction, of unsaturated functional groups, in particular with at least one radically polymerizable carbon-carbon double bond, for example of methacrylate groups and / or an acrylate group and / or a vinyl group and / or allyl group and / or an ethenylene group, on the hybrid layer with unsaturated, functional groups, in particular with at least one radically polymerizable carbon-carbon double bond, for example of methacrylate Groups and / or an acrylate group and / or a vinyl group and / or allyl group and / or an ethenylene group can be formed on the thermoset plastic or on the resin for forming the thermoset plastic.

A covalent connection of the hybrid layer with the thermosetting plastic via amine units can be achieved, for example, by an addition reaction of amino groups on the hybrid layer with epoxy groups on the thermosetting plastic or on the resin to form the thermosetting plastic, or vice versa, by an addition reaction of epoxy groups on the hybrid layer with amino groups on the thermosetting plastic or on the resin for forming the thermosetting plastic.

A covalent connection of the hybrid layer with the thermosetting plastic via ether units can be achieved, for example, by an addition reaction and / or by a condensation reaction of hydroxyl groups and / or epoxy groups on the hybrid layer with epoxy groups and / or hydroxyl groups on the thermosetting plastic Plastic or be formed on the resin to form the thermosetting plastic.

A covalent connection of the hybrid layer with the thermosetting plastic via thioether units can be achieved, for example, by an addition reaction of thiol groups on the hybrid layer with epoxy groups on the thermosetting plastic or on the resin to form the thermosetting plastic, or vice versa, by an addition reaction of epoxy groups on the hybrid layer with thiol groups on the thermosetting plastic or on the resin for forming the thermosetting plastic. A covalent connection of the hybrid layer with the thermosetting plastic via carboxylic acid ester units can be achieved, for example, by an addition reaction and / or by an esterification reaction of carboxylic acid groups on the hybrid layer with epoxy groups and / or hydroxyl groups on the thermosetting plastic or on the resin Formation of the thermosetting plastic, or vice versa, be formed by an addition reaction and / or by an esterification reaction of epoxy groups and / or hydroxyl groups on the hybrid layer with carboxylic acid groups on the thermosetting plastic or on the resin to form the thermosetting plastic .

In a further embodiment, the organic proportion of the hybrid layer increases from the component to the thermoset plastic. For example, the concentration of the at least one functional group and / or the at least one further functional group and / or their decomposition products can increase from the component in the direction of the thermoset plastic. In this way, the advantageous properties of the hybrid layer, in particular with regard to the promotion of adhesion and also corrosion protection and / or impermeability, can be further improved.

The hybrid layer can, for example, have an average layer thickness in a range of 0.1 5 sen.

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

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

In the context of a further embodiment, the component comprises or is an electronic and / or electrical component. For example, the component can be a sensor, for example a current sensor and / or battery sensor, or a component of a sensor, for example a shunt, for example made of copper and / or a resistance alloy such as resist, for a sensor, for example a current sensor and / or battery sensor, and / or an electronic circuit, for example which silicon chips and / or low-temperature burn-in ceramics (LTCC; English: Low Temperature Cofired Ceramics) and / or a circuit board, for example a circuit board equipped with electronics, and / or a, in particular electronic, control device, and / or a flow concentrator and / or a, in particular electrical, conductor, for example a phase connector and / or a phase tap.

In the context of a further embodiment, the thermosetting plastic comprises at least one shrinkage-reducing, in particular shrinkage-inhibiting, additive, and / or at least one filler and / or at least one fire-retardant and / or flame-retardant additive.

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

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

The component-plastic composite can, for example, be a sealed packaging, for example in which the component is packed tightly, in particular liquid-tight, for example watertight, and / or moisture-tight and / or gas-tight, in particular media-tight, through the hybrid layer and the thermosetting plastic applied to it. Component-plastic composites according to the invention and component-plastic composites produced according to the invention can be characterized and / or detected by infrared reflection spectroscopy (ATR) and / or interference reflectometry. For example, the hybrid layer can be characterized and detected by 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, for example on metal or plastic surfaces, for example in the form of a characteristic fingerprint, can be detected by infrared reflection spectroscopy, be detected. For example, the layer thickness can be determined by reflection spectroscopy.

With regard to further technical features and advantages of the component / plastic composite according to the invention, explicit reference is hereby made to the explanations in connection with the method according to the invention and to the figure, the description of the figures and the exemplary embodiments.

Drawing and examples

Further advantages and advantageous configurations of the subject matter according to the invention are illustrated by the drawing and the exemplary embodiments and explained in the following description. It should be noted that the drawing and the exemplary embodiments are only of a descriptive character and are not intended to restrict the invention in any form. It shows

1 shows a schematic cross section through an embodiment of a component / plastic composite according to the invention.

FIG. 1 shows that the component / plastic composite 10 comprises a component 11. In this case, the component 11 is at least partially covered with, in particular silicon- and oxygen-containing, partially inorganic and partially organic Hybrid layer 12 coated. A thermosetting plastic 13 is applied to the hybrid layer 12.

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

The hybrid layer 12 can, for example, comprise or be formed from siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide, for example organic-inorganic hybrid polymers with siloxane structures and / or silsesquioxane structures and / or regions of amorphous silicon dioxide. The hybrid layer 12 can in particular be formed by means of a coating process which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, for example by chemical vapor deposition from a gas phase, which includes at least one organosilicon compound as a precursor.

The thermosetting plastic 13 is formed by applying a resin formulation to form a thermosetting plastic, for example an unsaturated polyester resin and / or a vinyl ester resin and / or an epoxy resin, on the hybrid layer 12 and by curing the resin formulation.

The hybrid layer 12 can be connected to the thermosetting plastic 13 via covalent bonds (not shown).

Embodiments

A test series of previously cleaned components made of copper was carried out in a reactor at atmospheric pressure and at a temperature of 300 ° C chemical vapor deposition (CVD; English: Chemical Vapor Deposition) each coated with a, in particular silicon and oxygen-containing, partially inorganic and partially organic hybrid layer.

The gas phase from which the hybrid layer was deposited contained approximately 95% by volume of forming gas, consisting of 95% by volume of nitrogen and 5% by volume of hydrogen, as well as acetic acid, water and, as silicon-containing precursors, tetramethylorthosilicate, 3-aminopropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate. The total proportion of all silicon-containing precursors in the gas phase was between 0.5 and 1.0% by volume, with tetramethylorthosilicate forming more than half of this total proportion of silicon-containing precursors. 3-aminopropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate were present in a volume ratio of approximately 2: 1 in the gas phase. Based on the volume fraction of water, acetic acid was added in excess, but not more than in a ratio of 2: 1.

An unsaturated polyester resin was applied to the hybrid layers to form a thermosetting plastic in the form of frustoconical test specimens and cured to form the thermosetting plastic.

As a reference, the unsaturated polyester resin for forming the thermosetting plastic in the form of frustoconical reference test specimens was applied to uncoated, cleaned, similar components made of copper and cured to form the thermosetting plastic.

Some of the samples were subjected to a climate change test, in particular with a temperature changing between -30 ° C to + 160 ° C and a relative humidity changing between 10% to 95% over 6 days.

The adhesive strength of the test specimens and reference test specimens was then determined with and without a previous climate change test.

The test specimens without the alternating climate test had almost twice as high an adhesive strength as the reference test specimens without the alternating climatic test. And even after the alternating climate test, the test specimens with alternating climatic test showed an adhesive strength of more than 30% higher than the reference test specimens without alternating climatic test. The test specimens subjected to the alternating climate test showed, as did the

Test specimen without climate change test, no corrosion.

The reference test specimens subjected to the alternating climate test showed significant corrosion and failure of adhesion during the alternating climatic test.

Claims

Expectations

1. A method for producing a component-plastic composite (10), comprising the process steps: a) coating a component (11) with a, in particular silicon- and oxygen-containing, partially inorganic and partially organic hybrid layer (12) by means of a coating process which comprises a chemical reaction of at least one organosilicon compound as a precursor and a deposition process from a gas phase, b) applying a resin formulation to form a thermosetting plastic (13) on the hybrid layer (12) and c) curing the resin formulation to form the thermosetting plastic (13).

2. The method according to claim 1, wherein the coating in method step a) takes place by means of chemical vapor deposition from a gas phase comprising at least one organosilicon compound as a precursor.

3. The method according to claim 1 or 2, wherein in method step a) the gas phase comprises at least one organosilicon compound with at least one functional group as a precursor and a partially inorganic and partially organic hybrid layer (12) with at least one functional group is formed, and wherein in method step b) the resin formulation comprises a resin with at least one repeating unit with at least one functional group, a covalent bond being formed by a reaction of the at least one functional group of the hybrid layer (12) with the at least one functional group of the at least one repeating unit of the resin.

4. The method according to any one of claims 1 to 3, wherein the coating in process step a) at a temperature in a range of 200 ° C

400 ° C, in particular 250 350 ° C, takes place.

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

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

7. The method according to any one of claims 3 to 6, wherein the at least one functional group of the hybrid layer (12) and / or the at least one organosilicon compound is an unsaturated, functional group, in particular with 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 a Comprises or is 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 the at least one organosilicon compound is a methacrylate group and / or an acrylate group and / or a vinyl group and / or an ethenylene group and / or an amino group and / or a hydroxyl group and / or a thiol group and / or a thion urethane group and / or a thiol urethane group and / or a dithiourethane group and / or a Comprises or is a carboxylic acid group and / or an epoxide 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. The 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 the at least one functional group of the hybrid layer (12) and / or the at least one organosilicon compound is bonded to silicon via a silicon-carbon bond.

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

12. The method according to claim 11, wherein the at least one organosilicon compound with the at least one functional group comprises a methacrylate group and / or an acrylate group as functional group, and wherein the at least one further organosilicon compound with the at least one further functional group is an amino -Group and / or an isocyanate group as a further functional group, in particular wherein the hybrid layer (12) comprises a reaction product from an addition reaction, in particular a Michael addition, an amino group to the methacrylate group and / or acrylate group .

13. The method according to any one of claims 1 to 12, wherein the gas phase in method step a) further comprises at least one silicic acid ester, in particular ortho-silicic acid ester.

14. The method according to any one of claims 1 to 13, wherein the gas phase in method step a) further comprises at least one unfunctionalized organosilicon compound, in particular at least one silicic acid ester, wherein preferably during method step a) in the gas phase the concentration of the at least one organosilicon compound with the at least one functional group and / or the concentration of the at least one further organosilicon compound with the at least one further functional group is increased and / or the concentration of the at least one unfunctionalized organosilicon compound is reduced.

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 the at least one functional group of the at least one repeating unit of the resin is an unsaturated, functional group, in particular with at least one radically polymerizable carbon-carbon double bond, and / or an epoxy group and / or comprises or is a hydroxyl group.

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

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

- At least one shrinkage-reducing additive, and / or

- At least one filler, and / or

- At least one fire-retardant and / or flame-retardant additive.

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

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

21. Component-plastic composite (10), comprising a component (11), wherein the component (11) is at least partially coated with a, in particular silicon- and oxygen-containing, partially inorganic and partially organic hybrid layer (12) and wherein on the Hybrid layer (12) a thermosetting plastic (13) is applied.

22. Component-plastic composite (10) according to claim 21, wherein the hybrid layer (12) is connected to the thermosetting plastic (13) via covalent bonds.

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

24. Component-plastic composite (10) according to one of claims 21 to 23, wherein the hybrid layer (12) over

- Alkylene units and / or

- Amine units and / or

- Ether units and / or

- thioether units and / or

- Carboxylic acid ester units are covalently bonded to the thermoset plastic (13).

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

26. Component-plastic composite (10) according to one of claims 21 to 25, wherein the hybrid layer (12) siloxane structures and / or silsesquioxane structures and / or amorphous silicon dioxide, in particular organic inorganic hybrid polymers with siloxane structures and / or silsesquioxane -Structures and / or areas made of amorphous silicon dioxide.

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

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

29. Component-plastic composite (10) according to one of claims 21 to 28, wherein the thermoset plastic (13)

- At least one shrinkage-reducing additive, and / or

- At least one filler and / or

- at least one fire retardant and / or flame retardant additive, includes.

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