DE102015200425A1 - Reaction resin system with high thermal conductivity - Google Patents

Abstract

The present invention relates to a reaction resin system. To provide a reaction resin system with high thermal, mechanical and electrical stability and high thermal conductivity, the reaction resin system contains at least one thermally conductive filler and at least one cycloaliphatic epoxy resin and / or at least one cyanate ester. Moreover, the invention relates to an epoxy resin formulation, a cyanate ester formulation, as well as processes for their preparation and their use.

Description

The present invention relates to a reaction resin system, an epoxy resin formulation, a cyanate ester formulation, as well as processes for their preparation and their use.

State of the art

Reaction resin systems can be used for joining joining partners, for example a component and a substrate.

Conventional reaction resin systems, however, usually have a low thermal capacity, for example, of 180 ° C or less. In addition, conventional reaction resin systems typically have a low glass transition temperature (Tg), for example, of only about 40 ° C. In applications above the glass transition temperature (Tg), this can be problematic, since reaction resin systems, especially without fillers, above the glass transition temperature, high thermal expansion coefficients, for example of about 140 ppm / K, may have, in particular which are significantly higher than their expansion coefficient below the glass transition temperature, for example, of about 65 ppm / K.

Optionally, reaction resin systems - as well as uncrosslinked pastes - can be used for heat removal.

The pamphlets WO 2010/036953 A2 and US 5,972,246 A1 describe conductive resin compositions.

The pamphlets DE 10 2011 050 675 A1 . EP 2 098 571 A1 and EP 1 854 827 A1 concern cyanate-based resins.

The pamphlets US 2009/0298965 A1 . EP 0 307 665 A2 . US 2011/0315916 A1 and US 2012/0326301 A1 concern epoxy resin compositions.

Disclosure of the invention

The present invention is a reaction resin system, in particular for the production of a resin. The reaction resin system may be designed in particular for producing an epoxy resin and / or a cyanate ester resin.

The reaction resin system may in particular comprise at least one cycloaliphatic epoxy resin and / or at least one cyanate ester. In this case, the at least one cyanate ester may in particular comprise at least one polymeric cyanate ester and at least one monomeric cyanate ester.

A cycloaliphatic epoxy resin may, in particular, be understood as meaning a compound having at least one epoxide group, optionally having at least two epoxide groups, and having at least one cyclic, aliphatic group, optionally having at least two cyclic, aliphatic groups. For example, (in each case) an epoxide group can be attached to a cyclic, aliphatic group.

A cyanate ester may in particular be understood as meaning a compound, for example monomeric or polymeric, having at least two cyanate groups (-O-C≡N). Cyanate esters can advantageously crosslink and cure with one another via a so-called cyclotrimerization of three cyanate groups. The cyclotrimerization or curing reaction can be carried out in particular at elevated temperature, for example at a temperature of 150 ° C. to 280 ° C. By curing so-called thermosets can be formed.

A polymeric cyanate ester may, in particular, be understood as meaning a cyanate ester having at least one repeat unit having a repetition number of at least two, in particular of at least three. A polymeric cyanate ester may therefore also be an oligomeric cyanate ester.

In one embodiment, the reaction resin system further contains at least one polyorganosiloxane and / or at least one norbornene dicarboxylic anhydride-based curing agent.

A norbornene dicarboxylic anhydride-based curing agent may, in particular, be understood to mean a curing agent which comprises norbornene dicarboxylic anhydride and / or a norbornene dicarboxylic anhydride derivative, for example methyl norbornene-2,3-dicarboxylic anhydride.

In a particular embodiment, the reaction resin system may include an epoxy resin formulation containing at least one cycloaliphatic epoxy resin and, for example, at least one norbornene dicarboxylic anhydride based curing agent and / or a cyanate ester formulation containing at least one cyanate ester and, for example, at least one polyorganosiloxane.

Further objects of the invention are therefore also an epoxy resin formulation, in particular which contains at least one cycloaliphatic epoxy resin and, for example, at least one norbornene dicarboxylic anhydride-based curing agent, and a cyanate ester formulation, especially at least one cyanate ester, for example at least one polymeric cyanate ester and / or at least one monomeric cyanate ester, and, for example, at least one polyorganosiloxane. In this case, the epoxy resin formulation or the cyanate ester formulation can be designed in particular for the production of a reaction resin system according to the invention. In particular, the epoxy resin formulation or the cyanate ester formulation can be designed as explained in connection with the reaction resin system.

Within the scope of a further embodiment, the reaction resin system further contains at least one filler, for example at least one heat-conducting and / or electrically conductive filler, in particular at least one heat-conducting filler.

Such reaction resin systems can advantageously in the cured state - even in the case of an addition of fillers, especially at high degrees of filling - a high thermal stability or resilience and a high glass transition temperature (Tg) and a high mechanical and in particular electrical stability or load capacity and a relatively low have thermal expansion coefficients over a wide temperature range. Thus, it is advantageously possible to reduce thermal-mechanical stress on construction components, in particular even at high temperatures and during temperature changes, to provide sufficient viscoelastic properties and sufficient mechanical strength, for example to compensate for vibrations, and in this way to enable applications in a broad temperature operating range. Therefore, the reaction resin system can be used particularly advantageously in applications at high temperatures and / or under severe temperature changes.

In addition, such reaction resin systems can advantageously very high filler contents of fillers, in particular of more than 50 wt .-%, for example, of ≥ 70 wt .-%, bind.

The addition of a heat-conducting filler advantageously allows a sufficiently high thermal conductivity, for example of> 3.5 W / mK, to be achieved. Advantageously, such a reaction resin system, in particular with a high degree of filling, can be used as a heat conduction, in particular which - in contrast to conventional non-crosslinked thermal compounds, which usually also greatly expand at elevated temperatures, - can advantageously also serve as a means for mechanical fixation. Therefore, such a reaction resin system advantageously for cooling, and for example for mechanical fixation, are used.

In addition, the reaction resin system in the cured state may advantageously have a low dielectric constant. Therefore, the reaction resin system can be used particularly advantageously in high-performance electronics, for example for the cooling of high-performance electronics. Furthermore, resins formed from such reaction resin systems may advantageously have high media resistance, allowing their use in a wide range of applications.

Since in the curing reaction of the reaction resin system, for example, by a cyclotrimerization, hardly any or no volatile substances are eliminated, it is also advantageous particularly poorly or even defect-free body can be formed from this. The reaction resin system can therefore also be used particularly advantageously as potting compound.

In addition, it has surprisingly been found that the addition of a filler in the case of a cyanate ester formulation reduces the addition amount of a catalyst, or possibly even to the Addition of a catalyst can be omitted. In particular, therefore, the cyanate ester, optionally also the reaction resin system may be free of catalyst.

In a specific embodiment, the reaction resin system contains at least one heat-conductive filler. For example, the reaction resin system may be a thermally conductive reaction resin system or for producing a thermally conductive resin, for example, a thermally conductive cyanate ester resin and / or a thermally conductive epoxy resin designed.

A heat-conducting material, for example a heat-conductive filler, can be understood in particular to be a material, for example a filler, which has a specific thermal conductivity of ≥ 2 W / mK, in particular 10 W / mK, for example 20 W / mK ,

Within the scope of an embodiment, the at least one heat-conducting filler comprises silicon and / or aluminum oxide and / or a silicate, in particular an aluminum silicate, for example kyanite, and / or boron nitride and / or carbon nanotubes and / or silver and / or diamond powder. In particular, the at least one heat-conducting filler may comprise silicon and / or aluminum oxide and / or a silicate, in particular an aluminum silicate, for example kyanite, and / or boron nitride and / or carbon nanotubes, optionally in admixture with silver and / or diamond powder.

Using fillers, such as silicon powder, kyanite, boron nitride, carbon nanotubes - optionally in admixture with, for example, silver and / or diamond powder, advantageously crosslinking materials with thermal conductivity, for example of> 3.5 W / mK, high mechanical strength or less brittleness and high thermal capacity can be realized. Advantageously, the reaction resin system can thus be designed to be heat-conducting (overall). By using silicon and / or aluminum oxide and / or a silicate, in particular an aluminum silicate, for example kyanite, and / or boron nitride and / or carbon nanotubes, it is also possible advantageously to reduce material costs.

Optionally, the at least one thermally conductive filler may also be electrically conductive. In this case, the reaction resin system may in particular comprise at least one thermally conductive and electrically conductive filler. Optionally, the reaction resin system may additionally comprise at least one electrically conductive filler. An electrically conductive filler can advantageously achieve a low electrical resistance, for example of <0.9 mΩ · cm, and thus a sufficiently high electrical conductivity. For example, the reaction resin system can be designed to be (in total) electrically conductive and thermally conductive. Advantageously, such a reaction resin system, in particular with a high degree of filling, as, for example, lead-free, Lotersatzwerkstoff, in particular with no or at most a low Lotzerrüttung and - in contrast to conventional Lotmitteln - advantageously increased reliability, are used. For example, such a reaction resin system for cooling and for electrical contacting, and for example, for mechanical fixation, for example, a high-performance electronics, are used. The at least one electrically conductive filler may comprise, for example, silver and / or silicon and / or carbon nanotubes and / or silicon carbide and / or fullerene and / or copper and / or tin and / or zinc. By a blending can advantageously be adapted processing and / or functional properties. For example, this can be used to adapt the thermal expansion of the reaction resin system to that of silicon chips. For example, therefore, the at least one electrically conductive filler silver and at least one filler selected from the group consisting of silicon, carbon nanotubes, silicon carbide, fullerenes and mixtures thereof, and / or at least one filler selected from the group consisting of Copper, tin, zinc and mixtures thereof, in particular in the form of a mixture. By blending silver, optionally of different silver types, with alternative fillers, such as silicon powder, carbon nanotubes, silicon carbide or fullerene, advantageously the property profile for the application can be optimized. For example, the thermal expansion coefficient of the reaction resin system can thereby be adapted to that of semiconductor chips, for example silicon chips. In addition, by blending with such alternative fillers advantageously the material costs can be reduced. By a mixture or an addition of, for example, powdered, copper, tin and / or zinc advantageously also material costs can be reduced while maintaining a sufficient electrical conductivity. For example, the at least one electrically conductive filler may include or be formed from silver and silicon. This can be particularly advantageous for use as a solder substitute, in particular for semiconductor chips, for example silicon chips.

Within the scope of a specific embodiment, however, the at least one, in particular thermally conductive, filler is thermally conductive and electrically insulating, for example aluminum oxide and / or boron nitride, and / or the reaction resin system is heat-conducting and electrically insulating as a whole. By way of example, the reaction resin system may comprise a thermally conductive and (as a whole) electrically insulating filler mixture. By way of example, the at least one heat-conducting filler may comprise silicon and / or aluminum oxide and / or a silicate, in particular an aluminum silicate, for example kyanite, and / or boron nitride and / or carbon nanotubes, optionally in admixture with silver and / or diamond powder. An electrical conductivity can be achieved by the highest possible proportion of such, thermally conductive and electrically insulating filler / s, such as alumina and / or boron nitride, and in particular the smallest possible proportion of such, thermally conductive and electrically conductive filler / s, such as silver, be avoided.

The at least one filler may be uncoated or coated and may be, for example, splintery, spherical and / or platelet-shaped.

In a further embodiment, the reaction resin system, based on the total weight of the reaction resin system, a degree of filling of ≥ 30 wt .-% to ≤ 99 wt .-% of the at least one filler, in particular on the at least one thermally conductive filler, optionally on the at least a thermally conductive and / or electrically conductive filler, for example on the at least one heat-conductive filler and the at least one electrically conductive filler in total, for example on the at least one heat-conducting and electrically insulating filler. In particular, the reaction resin system, based on the total weight of the reaction resin system, a degree of filling of ≥ 45 wt .-% to ≤ 95 wt .-%, for example from ≥ 70 wt .-% to ≤ 80 wt .-%, of the at least one filler , in particular on the at least one heat-conducting filler, if appropriate on the at least one heat-conducting and / or electrically conductive filler, for example on the at least one heat-conducting filler and the at least one electrically conductive filler in total, for example on the at least one heat-conducting and electrically insulating filler , include. This has proved to be advantageous for achieving a high thermal conductivity and / or electrical conductivity. The reaction resin system can thus advantageously be used as a heat conduction, for example for the electrical contacting and / or heat dissipation of a high-performance electronics, and / or as, in particular lead-free, Lotersatzwerkstoff.

The reaction resin system, based on the total weight of the reaction resin system, for example, ≥ 1 wt .-% to ≤ 70 wt .-% of resin-forming components, for example on the epoxy resin formulation and / or cyanate ester formulation, optionally on the epoxy resin formulation and cyanate ester formulation in total. For example, the reactive resin system may contain ≥ 5% to ≤ 55%, for example ≥ 20% to ≤ 30% by weight, based on the total weight of the reactive resin system, of resin-forming components, such as the epoxy resin formulation and / or cyanate ester formulation, optionally on the epoxy resin formulation and cyanate ester formulation in total.

In the context of a further embodiment, the reaction resin system or the epoxy resin formulation contains at least one cycloaliphatic epoxy resin and at least one norbornene dicarboxylic anhydride-based curing agent.

In this case, a high thermal-mechanical stability can be achieved by the at least one norbornene dicarboxylic anhydride-based curing agent, wherein a sufficient fracture toughness can advantageously also be realized by the at least one cycloaliphatic epoxy resin. Such a composition can advantageously achieve a particularly high thermal stability or thermal resistance, in particular of ≥ 200 ° C., for example of about 230 ° C., of the cured epoxy resin. In addition, advantageously a particularly high glass transition temperature (Tg), in particular of ≥ 160 ° C., for example of ≥ 200 ° C., for example of about 210 ° C. or even 246 ° C., of the cured epoxy resin can be achieved. By virtue of such a high glass transition temperature, a high mechanical stability or load-bearing capacity, for example a relatively high fracture toughness or a low brittleness, can advantageously be achieved over a broad temperature range, in particular even at high fill levels. Advantageously, a low coefficient of thermal expansion can thus also be achieved in a wide temperature working range. Thus, it is advantageously possible to reduce thermal-mechanical stress on construction components, in particular even at high temperatures and during temperature changes, to provide sufficient viscoelastic properties and sufficient mechanical strength, for example to compensate for vibrations, and in this way to enable applications in a broad temperature operating range. Furthermore Such reaction resin systems or formulations can advantageously bind very high fillers to fillers, in particular of more than 50% by weight, for example of ≥70% by weight. In addition, such reaction resin systems or formulations in the cured state can advantageously have a low dielectric constant. Therefore, such reaction resin systems or formulations can be used particularly advantageously in high-performance electronics. Furthermore, resins formed from reaction resin systems or formulations of this type can advantageously have a high resistance to media, which enables their use in a wide range of applications.

In a further embodiment, the at least one cycloaliphatic epoxy resin comprises or is an epoxycycloalkyl carboxylate, for example an epoxycyclohexyl carboxylate. For example, the at least one cycloaliphatic epoxy resin may comprise or be an epoxycycloalkyl-alkylcarboxylate, for example an epoxycycloalkyl-methylcarboxylate. In particular, the at least one cycloaliphatic epoxy resin may be a bis (epoxycycloalkyl) carboxylate and / or bis (epoxycycloalkyl) alkyl carboxylate, for example a bis (epoxycyclohexyl) carboxylate and / or bis (epoxycycloalkyl) methylcarboxylate, for example bis (epoxycyclohexyl) Methylcarboxylate, such as Celloxide 2021P from Daicel or Araldit CY 179 from Huntsman. This has proved to be particularly advantageous in terms of achieving the already explained properties.

The at least one norbornene dicarboxylic anhydride-based hardener can be, for example, methyl norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride), such as 1-methyl-5-norbornene-2,3-dicarboxylic anhydride, for example HY 906 from Huntsman, and / or 8, 9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride (nadic acid anhydride) include.

In a further embodiment, the at least one norbornene dicarboxylic anhydride based curing agent comprises or is methyl norbornene-2,3-dicarboxylic anhydride. This has proved to be particularly advantageous in terms of achieving the already explained properties.

In the context of one embodiment of this embodiment, the at least one norbornene dicarboxylic anhydride-based curing agent comprises or is a mixture of methyl norbornene-2,3-dicarboxylic anhydride (1-methyl-5-norbornene-2,3-dicarboxylic acid anhydride) and 8,9,10- trinorborn-5-en-2,3-dicarboxylic anhydride. In particular, the at least one norbornene dicarboxylic anhydride-based hardener, based on the total weight of the at least one norbornene dicarboxylic anhydride-based hardener, may contain ≥ 70% by weight to ≤ 90% by weight of methyl norbornene-2,3-dicarboxylic anhydride and ≥ 10% by weight. % to ≤ 30% by weight of 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride. This has proved to be particularly advantageous in terms of achieving the already explained properties.

In a further embodiment, the amount of the at least one cycloaliphatic epoxy resin to the amount of at least one Norbornendicarboxylanhydrid-based curing agent in a weight ratio of 100: 90 to 100: 130, for example from 100: 90 or 100: 100 to 100: 110 or 100 : 120, for example, from about 100: 100 or 100: 109 or 100: 110. Thus, advantageously, the moisture absorption can be reduced.

For example, the reaction resin system based on the total weight of the resinous components of the reaction resin system or the epoxy resin formulation based on the total weight of the epoxy resin formulation may comprise ≥25 wt% to ≤70 wt% of the at least one cycloaliphatic epoxy resin. In particular, based on the total weight of the resin-forming components of the reaction resin system, or the epoxy resin formulation based on the total weight of the epoxy resin formulation, the reaction resin system may contain ≥35 wt% to ≤60 wt%, for example ≥40 wt% to ≦ 55% by weight, for example ≥ 47% by weight to ≦ 53 Wt .-%, for example by about 50 wt .-%, comprising at least one cycloaliphatic epoxy resin. Thus, advantageously, a balanced property profile can be achieved.

For example, the reaction resin system based on the total weight of the resinous components of the reaction resin system or the epoxy resin formulation based on the total weight of the epoxy resin formulation may comprise ≥30 wt% to ≤75 wt% of the at least one norbornene dicarboxylic anhydride based curing agent , In particular, the reaction resin system based on the total weight of the resin-forming components of the reaction resin system or the epoxy resin formulation based on the total weight of the epoxy resin formulation can be ≥ 40 wt% to ≤ 65 wt%, for example ≥ 45 wt% to ≤ 60 wt .-%, for example, ≥ 47 wt .-% to ≤ 53 wt .-%, for example by about 50 wt .-%, comprising at least one Norbornendicarboxylanhydrid-based hardener. Thus, advantageously, a balanced property profile can be achieved. Optionally, the amount of the at least one norbornene dicarboxylic anhydride based curing agent may exceed the amount of the at least one cycloaliphatic epoxy resin.

Optionally, the reaction resin system or the epoxy resin formulation may further comprise at least one accelerator. The at least one accelerator may, for example, comprise or be formed from an imidazole-based accelerator, for example an imidazole, for example 1-methylimidazole.

For example, based on the total weight of the resin-forming components of the reaction resin system, or the epoxy resin formulation based on the total weight of the epoxy resin formulation, the reaction resin system may contain 0 wt.% To ≦ 2 wt.%, For example ≥ 0.01 wt. to ≦ 2% by weight, comprising at least one accelerator. In particular, the reaction resin system based on the total weight of the resin-forming components of the reaction resin system or the epoxy resin formulation based on the total weight of the epoxy resin formulation can be ≥ 0 wt.% To ≦ 1 wt.%, For example ≥ 0.01 wt. to ≦ 1 wt .-%, to which include at least one accelerator So advantageously, the processing and reaction time can be tuned.

In the context of a further embodiment, the reaction resin system comprises - based on the total weight of the resin-forming components of the reaction resin system - or comprises the epoxy resin formulation - based on the total weight of the epoxy resin formulation - but ≥ 0 wt .-% to ≤ 2 wt .-%, in particular ≥ 0 wt .-% to ≤ 1 wt .-%, of accelerator. Thus, advantageously, a prolonged processing and reaction time can be achieved and, for example, thereby the processing, for example shaping, of the epoxy resin formulation or of the reaction resin system can be improved.

In a further embodiment, the amount of the at least one cycloaliphatic epoxy resin to the amount of at least one accelerator in a weight ratio of 100: 0.1 to 100: 3, in particular from 100: 0.1 or 100: 1 to 100: 2, for example, from about 100: 1.5 or 100: 0.3. Thus, advantageously, the processing and reaction time can be adjusted.

In a further embodiment, the amount of the at least one norbornene dicarboxylic anhydride-based curing agent is in the amount of the at least one accelerator in a weight ratio of 100: 0.1 to 100: 3, in particular of 100: 0.1 or 100: 1 to 100: 2, for example of about 100: 1.5 or 100: 0.3. Thus, advantageously, the processing and reaction time can be adjusted.

In particular, the amount of the at least one cycloaliphatic epoxy resin, the amount of the at least one norbornene dicarboxylic anhydride based curing agent, and the amount of the at least one promoter based on the total weight of the epoxy resin formulation may add up to less than or equal to 100% by weight. In particular, the amount of the at least one cycloaliphatic epoxy resin, the amount of the at least one norbornene dicarboxylic anhydride based curing agent, and the amount of the at least one accelerator, based on the total weight of the epoxy resin formulation, may add up to 100% by weight.

In another embodiment, the reaction resin system or the cyanate ester formulation contains at least one polymeric cyanate ester, at least one monomeric cyanate ester and at least one polyorganosiloxane.

In a further embodiment, the amount of the at least one polymeric cyanate ester is the amount of the at least one monomeric cyanate ester in a weight ratio of 8: 1 to 12: 1. In particular, the amount of the at least one polymeric cyanate ester may be in the amount of the at least one monomeric cyanate ester in a weight ratio of 9: 1 to 11: 1, for example about 10: 1.

Such a high proportion of polymeric cyanate ester may advantageously have a particularly high thermal stability or thermal resistance, in particular of ≥ 200 ° C., for example of ≥ 225 ° C. or even ≥ 250 ° C., for example of about 280 ° C., of the cured cyanate ester resin be achieved. In addition, advantageously, a particularly high glass transition temperature (Tg), in particular of ≥ 225 ° C, for example of ≥ 250 ° C, for example of about 260 ° C, of cured cyanate ester resin can be achieved. By means of such a high glass transition temperature, a high mechanical and electrical stability or load-bearing capacity, for example a relatively high fracture toughness or low brittleness, can advantageously be achieved over a wide temperature range, in particular even at high fill levels. Advantageously, a low coefficient of thermal expansion can thus also be achieved in a wide temperature working range. Thus, it is advantageously possible to reduce thermal-mechanical stress on construction components, in particular even at high temperatures and during temperature changes, to provide sufficient viscoelastic properties and sufficient mechanical strength, for example to compensate for vibrations, and in this way to enable applications in a broad temperature operating range. Moreover, such reaction resin systems or formulations can advantageously bind very high fillers to fillers, in particular of more than 50% by weight, for example of ≥ 70% by weight. In addition, such reaction resin systems or formulations in the cured state can advantageously have a low dielectric constant. Therefore, such reaction resin systems or formulations can be used particularly advantageously in high-performance electronics. Furthermore, resins formed from reaction resin systems or formulations of this type can advantageously have a high resistance to media, which enables their use in a wide range of applications.

In a further embodiment, the amount of the at least one monomeric cyanate ester to the amount of the at least one polyorganosiloxane in a weight ratio of 1: 1 to 2: 1. In particular, the amount of the at least one monomeric cyanate ester may be in the amount of the at least one polyorganosiloxane in a weight ratio of from 1.4: 1 to 1.7: 1, for example from 1.5: 1 to 1.6: 1. Thus, advantageously, the thermal and mechanical stability or load capacity can be further increased.

In a further embodiment, the reaction resin system or the cyanate ester formulation, in particular based on the total weight of the resin-forming components of the reaction resin system or based on the total weight of the cyanate ester formulation, ≥ 70 wt .-% to ≤ 99 wt .-% of the at least one polymeric cyanate ester. Thus, advantageously, the thermal and mechanical stability or load capacity can be further increased. In particular, the reaction resin system based on the total weight of the resin-forming components of the reaction resin system or the cyanate ester formulation based on the total weight of the cyanate ester formulation can be ≥ 75% to ≦ 95% by weight, for example ≥ 80% by weight to ≦ 90% by weight comprising at least one polymeric cyanate ester. Thus, advantageously, the thermal and mechanical stability or load capacity can be further optimized.

The reaction resin system may comprise, based on the total weight of the resin-forming components of the reaction resin system, or the cyanate ester formulation, based on the total weight of the cyanate ester formulation, for example ≥ 0.1% to ≤ 20% by weight of the at least one monomeric cyanate ester. In particular, the reaction resin system based on the total weight of the resin-forming components of the reaction resin system or the cyanate ester formulation based on the total weight of the cyanate ester formulation can be ≥ 2 wt% to ≤ 15 wt%, for example ≥ 8 wt% to ≤ 9 % By weight, comprising at least one monomeric cyanate ester. Thus, advantageously, the thermal and mechanical stability or load capacity can be further optimized.

On the at least one polyorganosiloxane, the reaction resin system may comprise, based on the total weight of the resin-forming components of the reaction resin system or the cyanate ester formulation based on the total weight of the cyanate ester formulation, for example ≥ 0.1% to ≤ 20% by weight. In particular, based on the total weight of the resin-forming components of the reaction resin system, or the cyanate ester formulation based on the total weight of the cyanate ester formulation, the reaction resin system may contain ≥1 wt% to ≤10 wt%, for example ≥5 wt% to ≤ 6 wt .-%, comprising at least one polyorganosiloxane. Thus, advantageously, the thermal and mechanical stability or load capacity can be further optimized.

Based on the total weight of the cyanate ester formulation, the amount of the at least one polymeric cyanate ester, the amount of the at least one monomeric cyanate ester and the amount of the at least one polyorganosiloxane, for example, in total less than or equal to 100 wt .-%. In particular, the amount of the at least one polymeric cyanate ester, the amount of the at least one monomeric cyanate ester, and the amount of the at least one polyorganosiloxane, based on the total weight of the cyanate ester formulation, may add up to 100 weight percent.

For example, the cyanate ester formulation based on the total weight of the cyanate ester formulation,
≥ 70 wt .-% to ≤ 99 wt .-%, for example ≥ 75 wt .-% to ≤ 95 wt .-%, in particular ≥ 80 wt .-% to ≤ 90 wt .-%, of the at least one polymeric cyanate ester .
≥ 0.1 wt .-% to ≤ 20 wt .-%, for example ≥ 2 wt .-% to ≤ 15 wt .-%, in particular ≥ 8 wt .-% to ≤ 9 wt .-%, of the at least one monomeric cyanate ester and
≥ 0.1 wt .-% to ≤ 20 wt .-%, for example ≥ 1 wt .-% to ≤ 10 wt .-%, in particular ≥ 5 wt .-% to ≤ 6 wt .-%, of the at least one Polyorganosiloxane include, in particular wherein the amount of the at least one polymeric cyanate ester, the amount of the at least one monomeric cyanate ester and the amount of the at least one polyorganosiloxane, based on the total weight of the cyanate ester formulation, in total less than or equal to 100 wt .-%, in particular 100% by weight.

In a further embodiment, the at least one polymeric cyanate ester comprises or is a polyphenol cyanate. In particular, the at least one polymeric cyanate ester may comprise or be oligo (3-methylene-1,5-phenylcyanoate).

The at least one monomeric cyanate ester may, for example, be selected from the group of bisphenol-based cyanate esters and novolac-based cyanate esters. Examples of bisphenol-based cyanate esters are bisphenol E-cyanate esters such as 4,4-ethylidenediphenylcyanate ester, bisphenol A cyanate ester, hexafluorobisphenol A cyanate ester, tetramethylbisphenol F-cyanate ester, bisphenol M-cyanate ester, bisphenol C-cyanate ester and Cyclopentadienylbisphenolcyanatester. Examples of novolac-based cyanate esters are novola cyanate esters and phenol novolacanate esters, respectively.

In a further embodiment, the at least one monomeric cyanate ester comprises or is a bisphenol-based cyanate ester. Bisphenol-based cyanate esters have proven to be advantageous for achieving a high thermal and mechanical stability or load capacity.

In a specific embodiment of this embodiment, the at least one monomeric cyanate ester comprises or is a bisphenol-E-based cyanate ester, in particular bisphenol-E-dicyanate. Bisphenol E-based cyanate esters have proven to be particularly advantageous for achieving high thermal and mechanical stability or loading capacity.

The at least one polyorganosiloxane may in particular comprise a rubber-elastic polymer, for example having a glass transition temperature in a range from ≥ -80 ° C to ≦ -40 ° C, and / or for forming a rubber-elastic polymer, for example having a glass transition temperature in a range of ≥ -80 ° C to ≤ -40 ° C, designed by cross-linking.

For example, the at least one polyorganosiloxane can be derivable from the general chemical formula: - (R ₂ SiO) -. The two radicals R may be the same or different and may be bonded directly or indirectly via an oxygen atom or a nitrogen atom to the silicon atom. For example, the two radicals R can each independently be a linear or branched alkyl group having 1 to 18 carbon atoms, for example a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dodecyl and / or octadecyl group or a cycloalkyl group having 4 to 8 carbon atoms, for example, a cyclopentyl, cyclohexyl and / or cyclooctyl group, or a linear or branched alkenyl group having 2 to 4 carbon atoms, for example, a vinyl, allyl, isopropenyl and / or 3 -Butenyl group, or a phenyl group or an alkylphenyl group with a substituted, in particular halogen, hydroxyl, carboxyl, carboxylic anhydride, amino, epoxy, alkoxy and / or alkenyloxy-substituted, or unsubstituted alkyl radical having 1 to 12 Carbon atoms, for example an ethylphenyl group, or a polyether group, for example a polyethylene oxide, polypropylene oxide, polybutylene oxide, polyhexamethylene glycol and / or P polytetrahydrofuran group, or a polyolefin group, for example a polyethylene, polypropylene, polybutadiene, polyisoprene, polybutene and / or polyisobutene group, or hydrogen. The groups may optionally be partially substituted, for example, with one or more halogen atoms, such as fluorine and / or chlorine, such as a chloropropyl or 1,1,1-trifluoropropyl group, be. The radicals R may be the same or different radicals, for example, which may be randomly distributed along the siloxane chain. The at least one polyorganosiloxane may optionally also comprise or be a mixture of such polyorganosiloxanes.

For example, the at least one polyorganosiloxane may comprise or be a block copolymer, which may, for example, be derivable from the general chemical formula: - (R ' ₂ SiO) _x - (R " ₂ SiO) _y -. Here, x and y can each stand for the repetition number and be equal to 1 or an integer multiple thereof. R 'and R''may be connected directly or indirectly via an oxygen atom or a nitrogen atom to the silicon atom and stand for different from each other in connection with R illustrated groups.

For example, at least 50% of the radicals R or R 'and / or R "may be a methyl group and / or phenyl group. Such polyorganosiloxanes can advantageously be readily available and achieve a good effect.

Optionally, the radicals R or R 'and / or R "may be selected in view of a sufficient dispersibility of the at least one polyorganosiloxane in the at least one monomeric cyanate ester and / or in the at least one polymeric cyanate ester. Thus, advantageously, an addition of a dispersant can be avoided.

In a further embodiment, the at least one polyorganosiloxane is present in the form of, in particular solid or liquid, polyorganosiloxane particles in the reaction resin system, in particular in the cyanate ester formulation. For example, the Polyorganosiloxanteilchen in finely divided form in the reaction resin system, for example in the cyanate ester formulation or in the at least cyanate ester, in particular in the at least one monomeric cyanate ester may be included.

The polyorganosiloxane particles may have, for example, an average diameter of ≥ 0.01 μm to ≦ 50 μm, in particular of ≥ 0.05 μm to ≦ 20 μm, for example of ≥ 0.1 μm to ≦ 5 μm. Thus, advantageously, the fracture and impact resistance can be further improved. The polyorganosiloxane particles may have both a unimodal and a bimodal or trimodal or multimodal particle size distribution. In particular, the polyorganosiloxane particles may have a broad particle size distribution, for example over the entire range of ≥ 0.1 μm to ≤ 5 μm. In this case, a broad distribution of the particle size can be realized both by a broad unimodal distribution and by a bimodal or trimodal or multimodal distribution, for example of respectively narrower size distributions.

As explained in more detail in connection with the preparation process according to the invention, the at least one monomeric cyanate ester and the at least one polyorganosiloxane can be used in particular in the form of a dispersion which contains the at least one monomeric cyanate ester and, in particular solid or liquid, polyorganosiloxane particles from the at least one polyorganosiloxane. Such dispersions may advantageously be characterized by a long shelf life. In this case, the at least one polyorganosiloxane may be crosslinked in the dispersion in particular to give a rubber-elastic polymer. The at least one monomeric cyanate ester may in particular be substantially uncrosslinked in the dispersion.

For example, the dispersion, based on the total weight of the dispersion, ≥ 40 wt .-% to ≤ 98 wt .-%, in particular ≥ 50 wt .-% to ≤ 98 wt .-%, comprising at least one monomeric cyanate ester. On the at least one polyorganosiloxane, the dispersion, based on the total weight of the dispersion, for example, ≥ 2 wt .-% to ≤ 60 wt .-%, in particular ≥ 2 wt .-% to ≤ 50 wt .-% include. In particular, the dispersion, based on the total weight of the dispersion, ≥ 2 wt .-% to ≤ 10 wt .-%, for example, ≥ 4 wt .-% to ≤ 8 wt .-%, comprising at least one polyorganosiloxane. Thus, advantageously good fracture mechanical properties can be achieved while maintaining a high modulus.

Optionally, the dispersion may further comprise at least one dispersant. By means of a dispersant, the dispersion can advantageously be stabilized. In addition, advantageously, the particle size can be influenced. The addition of a dispersant may be advantageous in particular in that an optimization of the at least one polyorganosiloxane with respect to the dispersibility would not be available or only consuming.

The at least one dispersant may in particular comprise or be a compound having an amphiphilic structure. For example, one part of the structure may be affine to the at least one polyorganosiloxane and another part of the structure may be affine to the at least one monomeric one Cyanate ester and / or to the at least one polymeric cyanate ester. For example, the at least one dispersant may be an emulsifier or emulsifier mixture.

For example, the at least one dispersing agent may comprise or be a copolymer of a polyorganosiloxane and another polymer, for example a polyether. The preparation of such copolymers is, for example, of W. Noll in "Chemistry and Technology of Silicones", Weinheim 1968 , described. The average molecular weight of the at least one dispersant can vary within wide limits. In particular, however, the at least one dispersant may have an average molecular weight in a range of ≥ 300 g / mol to ≦ 50,000 g / mol.

For example, the at least one dispersant can comprise or be a polyether-polydimethylsiloxane copolymer. The proportion of polydimethylsiloxane in the copolymer may be, for example, about 25% by weight, based on the total weight of the copolymer. The polyether of the copolymer may, for example, comprise ethylene oxide units and / or propylene oxide units. For example, the ethylene oxide units and the propylene oxide units may be present in a ratio of about 40% by weight to 60% by weight. For example, the copolymer may have an average molecular weight in a range ≥ 10,000 g / mol to ≤ 15,000 g / mol, for example of about 13,000 g / mol, and / or a viscosity at 25 ° C of ≥ 2,000 mPas to ≤ 4,000 mPas. Such copolymers have proven to be particularly advantageous for achieving a high storage stability.

For example, the dispersion, based on the total weight of the dispersion, ≥ 0 wt .-% to ≤ 20 wt .-%, for example ≥ 1 wt .-% to ≤ 15 wt .-%, comprising at least one dispersant.

The reaction resin system may in particular be free of polysilazanes.

Optionally, the at least one polyorganosiloxane may have functional groups which are reactive with functional groups of the at least one monomeric cyanate ester and / or the at least one polymeric cyanate ester, especially during the curing reaction to form a chemical bond. For example, the polyorganosiloxane particles may be surface modified with such functional groups. Thus, advantageously, the fracture and impact resistance can be further improved.

For example, the radicals R or R 'and / or R "of the at least one polyorganosiloxane can be substituted by functional groups.

Alternatively or additionally, the at least one dispersant and / or at least one reaction mediator may be provided with functional groups which have functional groups of the at least one polyorganosiloxane as well as functional groups of the at least one cyanate ester, for example the at least one monomeric cyanate ester and / or the at least one a polymeric cyanate ester, especially during the curing reaction, are reactive to form a chemical bond. For example, the at least one reaction agent can be an organoalkyloxysilane, for example vinyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, aminopiropyltriethoxysilane, methacryloyloxypropyltrimethoxysilane or the like, and / or an organosilicone copolymer with at least one polyorganosiloxane and at least one cyanate ester, for example at least one monomeric cyanate ester and or to the at least one polymeric cyanate ester, matched functional groups or be. For example, suitable organosilicone copolymers may, in principle, be similar to the dispersants described above. For example, it is possible to use organosilicone copolymers which are condensation products of low molecular weight silanol-terminated polydimethylsiloxanes with diglycidyl ethers, hydroxycarboxylic acids or polyesters containing hydroxyl and carboxylic acid groups and / or aromatic polyhydroxy compounds. Alternatively or additionally, suitable organosilicone copolymers can be prepared by hydrosilylation of polymethylhydrogensiloxanes with compounds which have the desired functional group and optionally additionally an olefinic double bond, such as allyl glycidyl ether, allyl alcohol, α-alkene alcohol-started polyethers, allyl methacrylate, 2-hydroxyethyl acrylate and / or maleic anhydride.

The reaction of the functional groups can be carried out in particular (briefly) before or during or after the further processing of the reaction resin system. For example, the reaction of the functional groups can be effected by a temperature increase and / or by the addition of the at least one reaction mediator and / or by the addition of a catalyst.

The curing of the cyanate esters and / or the reaction of the functional groups can be effected in particular simultaneously and / or by the same measure, for example by an increase in temperature and / or by the addition of a component, for example a catalyst. The curing of the cyanate esters and / or the reaction of the functional groups can be effected in particular after a shaping process.

Optionally, the reaction resin system may further comprise at least one catalyst. Thus, if necessary, the curing time and the course of the reaction can be better controlled. Optionally, the reaction resin system may comprise a transition metal catalyst, for example cobalt (II) acetylacetonate, for example dissolved in a bisphenol F epoxy resin, for example obtainable by reaction of bisphenol F and epichlorohydrin. For example, the reaction resin system, based on the total weight of the reaction resin system ≥ 0 wt .-% to ≤ 3 wt .-%, for example ≥ 0 wt .-% to ≤ 1.5 wt .-%, comprising at least one catalyst ,

Since it has surprisingly been found that a clearly catalyzing effect can be achieved by the addition of at least one filler, in the case of a cyanate ester, however, the reaction resin system or the cyanate ester formulation may in particular be free of catalyst.

The reaction resin system may, for example, based on the total weight of the reaction resin system, ≥ 1 wt .-% to ≤ 30 wt .-%, in particular ≥ 5 wt .-% to ≤ 25 wt .-%, for example ≥ 10 wt .-% to ≦ 25 wt .-%, of the at least one cycloaliphatic epoxy resin, and / or ≥ 1 wt .-% to ≤ 30 wt .-%, in particular ≥ 5 wt .-% to ≤ 25 wt .-%, for example ≥ 10 % By weight to ≦ 25% by weight, of which at least one norbornene dicarboxylic anhydride-based hardener, and / or ≥ 0% by weight to ≦ 1% by weight, for example ≥ 0% by weight to ≦ 0, 5 wt .-%, to the at least one accelerator, and / or ≥ 1 wt .-% to ≤ 30 wt .-%, in particular ≥ 15 wt .-% to ≤ 30 wt .-%, for example ≥ 20 wt. % to ≦ 25% by weight, of which at least one polymeric cyanate ester, and / or ≥ 0.1% by weight to ≦ 5% by weight, in particular ≥ 1% by weight to ≦ 4% by weight , for example ≥ 2 wt .-% to ≤ 3 wt .-%, of the at least one monomeric cyanate ester, and / or ≥ 0.1 wt .-% to ≤ 5 Ge % by weight, in particular ≥ 0.5% by weight to ≦ 3% by weight, for example ≥ 1% by weight to ≦ 2% by weight, of which at least one polyorganosiloxane comprises. In total, while the amount of the at least one cyanate ester - in particular the amount of the at least one polymeric cyanate ester and the amount of the at least one monomeric cyanate ester - the amount of the at least one polyorganosiloxane, the amount of the at least one cycloaliphatic epoxy resin, the amount on the at least one norbornene dicarboxylic anhydride-based hardener and the amount of the at least one accelerator in particular ≥ 1 wt .-% to ≤ 70 wt .-%, for example ≥ 5 wt .-% to ≤ 55 wt .-%, for example ≥ 20 Wt .-% to ≤ 30 wt .-%, based on the total weight of the reaction resin system, yield.

For example, the reaction resin system may comprise the epoxy resin formulation or the cyanate ester formulation or a combination of the epoxy resin formulation and the cyanate ester formulation.

Optionally, the reaction resin system may further comprise at least one epoxy resin and / or cyanate ester and / or polyurethane and / or polyester and / or acrylate, optionally in toughened form.

In particular, the reaction resin system may further comprise at least one epoxy resin and / or at least one cyanate ester - optionally in toughened form.

The reaction resin system can be used, for example, in the form of a paste, an adhesive, a lacquer or a potting compound, for example a so-called molding compound.

The reaction resin system or the cyanate ester formulation or the epoxy resin formulation may in particular be a curable material, for example a thermosetting material.

With regard to further technical features and advantages of the reaction resin system according to the invention, the inventive cyanate ester formulation and the epoxy resin formulation according to the invention, reference is hereby explicitly made to the explanations in connection with the inventive method and the use according to the invention and to the examples.

A further subject of the present invention is a process for the preparation of a reaction resin system and / or a cyanate ester formulation and / or an epoxy resin formulation. In particular, the method can be designed for the production of a reaction resin system according to the invention and / or a cyanate ester formulation according to the invention and / or an epoxy resin formulation according to the invention.

In particular, the resin-forming components can be mixed in the process. For example, at least one cyanate ester, for example at least one polymeric cyanate ester and / or at least one monomeric cyanate ester, and / or at least one cycloaliphatic epoxy resin and / or at least one polyorganosiloxane and / or at least one norbornene dicarboxylic anhydride-based curing agent can be mixed in the process.

In particular, at least one filler, for example at least one heat-conducting and / or electrically conductive filler, in particular at least one heat-conducting filler, can be admixed with it.

In a specific embodiment, at least one polymeric cyanate ester is mixed with a dispersion, for example emulsion containing at least one monomeric cyanate ester and, especially solid or liquid, polyorganosiloxane particles of at least one polyorganosiloxane. The polyorganosiloxane particles may be dispersed in particular in the at least one monomeric cyanate ester, in particular in finely divided form.

The dispersion can be prepared, for example, by first dispersing the at least one polyorganosiloxane, for example in liquid form, in the at least one monomeric cyanate ester or in a portion of the at least one monomeric cyanate ester and then adding a crosslinker for the at least one polyorganosiloxane. Optionally, it is possible to disperse a so-called pre-catalyzed polyorganosiloxane, that is, which already contains a catalyst, for example a platinum catalyst, in one part of the at least one monomeric cyanate ester and then to add another part of the at least one monomeric cyanate ester, before finally the crosslinker for the at least one polyorganosiloxane is added. By crosslinking the already dispersed polyorganosiloxane then the dispersed Polyorganosiloxanteilchen can be formed.

A fine distribution of, for example, liquid, polyorganosiloxanes in, for example, liquid, cyanate ester, for example, by measures and auxiliaries known for the preparation of dispersions or emulsions, for example mechanical aggregates with a sufficiently high shear in the medium to be dispersed, such as stirrer, dissolver, kneader , Roll mills, high pressure homogenizers, ultrasonic homogenizers and the like. For example, "Ultra Turrax" dispersing machines can be used to achieve a fine distribution.

The particle size distribution of the polyorganosiloxane particles can already be predetermined and controlled within the limits of the dispersion process in the formation of uncrosslinked polyorganosiloxane droplets by the selection of the shear forces and optionally the dispersant.

The average molecular weight of the at least one, for example liquid, for example uncrosslinked, polyorganosiloxane can vary within wide limits and, for example, in a range of ≥ 800 g / mol to ≤ 500,000 g / mol. Thus, on the one hand, sufficient elasticity and, on the other hand, an acceptable viscosity and thus a fine distribution of the polyorganosiloxane can advantageously be achieved. In particular, the at least one, for example liquid, for example uncrosslinked, polyorganosiloxane may have an average molecular weight in a range from ≥ 1000 g / mol to ≦ 100,000 g / mol, for example from ≥ 1,200 g / mol to ≦ 30,000 g / mol.

The crosslinking of the at least one, for example liquid, polyorganosiloxane to polyorganosiloxane particles can be effected, for example, by an addition crosslinking process and / or condensation crosslinking process, in particular an addition crosslinking process.

For addition crosslinking, the at least one polyorganosiloxane can have, in particular, a sufficient number of groups which have hydrogen bonded directly to silicon, ie SiH groups, and also olefinically unsaturated radicals which can be added to the SiH groups (hydrosilylation reaction). For example, a polydimethylsiloxane having vinyl end groups, for example, in which ≥0% to ≤10% by weight of a polymethylhydrogensiloxane is added as a crosslinker, may be used. The addition crosslinking can be carried out, for example, at room temperature, if appropriate also at an elevated temperature, for example at a temperature of ≥ 60 ° C. and ≦ 140 ° C., if appropriate in the presence of a catalyst, for example a noble metal catalyst. The catalyst may comprise, for example, at least one element of the platinum group, for example platinum, palladium and / or rhodium. For example, the catalyst may be hexachloroplatinic acid, for example, dissolved in a suitable solvent, such as glycol ether and / or isopropanol. Suitable catalysts may also be the reaction products of noble metal chlorides with organic or organosilicon compounds containing vinyl groups or the noble metals themselves in fine distribution on suitable carriers such as activated carbon or aluminum oxide.

For a condensation crosslinking, the at least one polyorganosiloxane may, for example, have at least one easily cleavable radical bonded directly to silicon, for example a hydroxyl, alkoxy, acyloxy, ketoximino, amine, aminoxy and / or alkylamide group or hydrogen. In this case, the at least one cleavable radical may be contained both in the at least one polyorganosiloxane and / or in silanes specifically added as crosslinker. For example, the at least one polyorganosiloxane can have a hydroxyl end group, with a tri- or tetraorganooxysilane, such as methyltriacetoxysilane, tetraethoxysilane, methyltris (methylethylketoximino) silane and / or polymethylhydrogensiloxane, being used as crosslinker. The catalyst used here can be organic heavy metal salts, such as octoates, laurates, naphthenates and / or acetates of tin, zirconium, lead and / or titanium.

However, as already explained, the use of a catalyst is not absolutely necessary.

A three-dimensional crosslinking of the at least one polyorganosiloxane can be achieved by addition and / or condensation crosslinking of functional groups attached both directly to the polyorganosiloxane chain and to an organic radical R or R 'and / or R' '.

Furthermore, the invention also relates to a reaction resin system and / or a cyanate ester formulation and / or an epoxy resin formulation prepared by such a process. For example, the reaction resin system according to the invention or the cyanate ester formulation of the invention or the epoxy resin formulation can be prepared by such a method.

Another object of the invention is a method for producing a resin. In particular, this method can be designed for producing a cyanate ester resin and / or an epoxy resin.

In particular, a reaction resin system according to the invention and / or a cyanate ester formulation according to the invention and / or a reaction resin system prepared according to the invention and / or a cyanate ester formulation prepared according to the invention and / or an epoxy resin formulation prepared according to the invention can be heated to a curing temperature of .gtoreq.150.degree. in particular from ≥ 200 ° C, for example from ≥ 250 ° C, are heated.

The invention therefore also relates to a resin, in particular a cyanate ester resin and / or an epoxy resin, which is produced by such a process.

With regard to further technical features and advantages of the inventive methods and their products, reference is hereby explicitly made to the explanations in connection with the reaction resin system according to the invention, the inventive cyanate ester formulation, the epoxy resin formulation according to the invention and the use according to the invention and the examples.

The invention further relates to the use of a reaction resin system according to the invention and / or a cyanate ester formulation according to the invention and / or an epoxy resin formulation according to the invention and / or a reaction resin system prepared according to the invention and / or a cyanate ester formulation prepared according to the invention and / or an epoxy resin formulation prepared according to the invention and / or a resin prepared according to the invention, in particular cyanate ester resin and / or epoxy resin, for electrical contacting and / or heat dissipation and / or mechanical fixation of a, in particular electrical or electronic, component, for example an electric vehicle, such as an electric motor vehicle, and / or a regenerative energy system and / or a High-power electronics, for example, a voltage converter and / or inverter and / or electric motor.

For example, the reaction resin system according to the invention and / or prepared according to the invention and / or cyanate ester formulation prepared according to the invention and / or the epoxy resin formulation according to the invention and / or the resin prepared according to the invention, in particular cyanate ester resin and / or epoxy resin, as, for example lead-free, Lotersatzwerkstoff be used. Thus, advantageously lead-containing solder, for example, in a high-performance electronics, such as a voltage converter, inverter and / or electric motor can be replaced. For this purpose, the reaction resin system may in particular comprise at least one electrically conductive filler. Thus, advantageously, a sufficient electrical contact can be realized.

Voltage transformers, inverters and electric motors can also have high self-heating. Optionally, therefore, the at least one electrically conductive filler also be thermally conductive.

The reaction resin system according to the invention and / or the invention and / or the cyanate ester formulation prepared according to the invention and / or the epoxy resin formulation according to the invention and / or the resin prepared according to the invention, in particular cyanate ester resin and / or epoxy resin, can also be used, for example, as heat transfer agents , and in addition, as a means of mechanical fixation, are used. For this purpose, the reaction resin system may in particular comprise at least one heat-conducting filler. Thus, advantageously, a highly efficient heat dissipation, for example in a high-performance electronics, such as a voltage converter, inverter and / or electric motor, can be realized. Optionally, a low electrical conductivity may be desired. Optionally, therefore, the at least one thermally conductive filler be electrically insulating.

With regard to further technical features and advantages of the use according to the invention and its products, reference is hereby explicitly made to the explanations in connection with the reaction resin system according to the invention, the cyanate ester formulation according to the invention, the epoxy resin formulation according to the invention and the methods according to the invention and the examples.

Examples

Further advantages and advantageous embodiments of the objects according to the invention are illustrated by the examples and explained in the following description. It should be noted that the examples are only descriptive and are not intended to limit the invention in any way.

1. filled cyanate ester with silicone modification

The following starting materials were used: Primaset PT30: Polyphenolcyanat; Oligo (3-methylene-1,5-phenyl-cyanate), Lonza, Switzerland Primaset LeCy: 4,4'-ethylidenediphenyl dicyanate, Lonza, Switzerland emulsifier: Polyether-polymethylsiloxane copolymer Polydimethylsiloxane content 25% by weight, ratio EO / PO units 40/60, MW 13,000 g / mol, viscosity at 25 ° C. 3,000 mPas Silicone VM: Premix of 99.5 wt .-% α, ω-Divinylpolydimethylsiloxan and 0.5 wt .-% of a 1% solution of hexachloroplatinic acid in 2-propanol crosslinkers: α, ω-di (trimethylsilyl) polymethylhydrogensiloxane fillers: AG 300-01 from Heraeus, Germany; Silver particles, D50 <5 μm CL 4400FG from Alcoa, Germany; Alumina particle D50 = 7 μm NO 625-10 from Nabaltec, Germany; Aluminum oxide particle D50 = 2.5 μm

1.1 Preparation of a silicone modifier

2500 g of Primaset LeCy and 660 g of emulsifier are mixed with stirring at 500 / min in a vacuum for 5 min. Then 2600 g of silicone-VM are added and dispersed in vacuo at 500 rpm for 25 minutes. Then 2500 g of Primaset LeCy are added and dispersed again for 15 minutes. Then 66.7 g of crosslinker are added and dispersed for another 10 min. A dispersion was obtained.

1.2 Preparation of Cyanate Ester Polyorganosiloxane Based Reaction Resin Systems

To Primaset PT30 is added the above-described silicone modifier and at least one filler. In the example CS1 silver particles are used as filler. In the example CS2, a mixture of alumina particles having an average particle diameter (D50) of 7 .mu.m and alumina particles having a mean particle diameter (D50) of 2.5 .mu.m is used as the filler. The quantitative ratios are given in Table 1. The materials were heated to a cure temperature of 250 ° C. Table 1: proportions of filled cyanate esters with silicone modification CS1 CS2 Primaset PT30; Polyphenolcyanat; Oligo (3-methylene-1,5-phenylencyanat) 23.2% by weight (tolerance: 20.88-25.52% by weight) 21.6% by weight (tolerance: 19.44-23.76% by weight) Silicone modifier from: Primaset LeCy; 4,4'-ethylenediphenyldicyanate and 2.3% by weight (tolerance: 2.07-2.53% by weight) 2.2% by weight (tolerance: 1.98-2.42% by weight) silicone 1.5% by weight (tolerance: 1.35-1.65% by weight) 1.4% by weight (tolerance: 1.26-1.54% by weight) Filling degree% 73% by weight 75% by weight Filler (e) Silver D50 <5 μm 73% by weight (tolerance: 70.3-75.7% by weight) Aluminum oxide D50 = 7 μm 52.5% by weight (tolerance: 50.60-54.12% by weight) and aluminum oxide D50 = 2.5 μm 22.5% by weight (tolerance: 21.68-23 , 2% by weight)

CS1 and CS2 had a glass transition temperature (Tg) of about 260 ° C and a thermal stability of about 280 ° C. CS1 had a high electrical conductivity and in particular also thermal conductivity. CS2 had acceptable thermal conductivity and high electrical resistance.

2. filled cycloaliphatic epoxy resins

The following starting materials were used: Cycloaliphatic epoxy resin: Celloxide 2021P from Daicel ((3 ', 4'-epoxycyclohexane) methyl-3,4-epoxycyclohexylcarboxylate) Harder: Mixture of 1-methyl-5-norbornene-2,3-dicarboxylic anhydride and 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride Accelerator: 1-methylimidazole

From the above starting materials, filled reaction resin systems were mixed as shown in Table 2 and heated to a curing temperature of 210 ° C. Table 2: proportions of the filled cycloaliphatic epoxy resins E1 E2 E3 Cycloaliphatic epoxy resin 18.1% by weight 18.05% by weight 14.1% by weight Harder 19.8% by weight 19.8% by weight 15.56% by weight accelerator 0.05% by weight 0.05% by weight 0.04% by weight Filling degree [%] 62 62.1 70.3 Filler (e) silver Silver 45.5% by weight Silicon 16.6% by weight silicon Glass transition temperature Tg [° C] 210 220 246 Thermal stability [° C] 230 230 230 Thermal expansion coefficient [ppm / K] <Tg> Tg 60 about 160 47 70 21 40-50 Specific electrical resistance [mΩ · cm] 3.4 18.2 > 1500000

E1, E2 and E3 advantageously had high glass transition temperatures, high thermal stabilities and lower thermal expansion coefficients. E1 had a high electrical conductivity and in particular also thermal conductivity. E2 had acceptable electrical conductivity and thermal conductivity. E3 had acceptable thermal conductivity and high electrical resistance.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2010/036953 A2 [0005]
• US 5972246 A1 [0005]
• DE 102011050675 A1 [0006]
• EP 2098571 A1 [0006]
• EP 1854827 A1 [0006]
• US 2009/0298965 A1 [0007]
• EP 0307665 A2 [0007]
• US 2011/0315916 A1 [0007]
• US 2012/0326301 A1 [0007]

Cited non-patent literature

• W. Noll in "Chemistry and Technology of Silicones", Weinheim 1968 [0072]

Claims (20)

Reaction resin system containing - At least one thermally conductive filler, and - At least one cycloaliphatic epoxy resin and / or - At least one cyanate ester. The reaction resin system of claim 1, wherein the reaction resin system further contains at least one polyorganosiloxane and / or at least one norbornene dicarboxylic anhydride based hardener. A reaction resin system according to claim 1 or 2, wherein the reaction resin system An epoxy resin formulation containing - At least one cycloaliphatic epoxy resin and At least one norbornene dicarboxylic anhydride based hardener, and / or A cyanate ester formulation containing At least one cyanate ester and At least one polyorganosiloxane, contains. Reaction resin system according to one of claims 1 to 3, wherein the reaction resin system, based on the total weight of the reaction resin system, a degree of filling of ≥ 30 wt .-% to ≤ 99 wt .-%, in particular from ≥ 45 wt .-% to ≤ 95 wt. -%, comprising at least one heat-conductive filler. Reactive resin system according to one of claims 1 to 4, wherein the at least one thermally conductive filler silicon and / or alumina and / or an aluminum silicate and / or boron nitride and / or carbon nanotube, in particular in admixture with silver and / or diamond powder comprises. Reaction resin system according to one of claims 1 to 5, wherein the at least one heat-conductive filler is thermally conductive and electrically insulating and / or wherein the reaction resin system is overall thermally conductive and electrically insulating. Reaction resin system according to one of claims 1 to 6, wherein the at least one cycloaliphatic epoxy resin is an epoxycycloalkyl carboxylate, in particular a bis (epoxycycloalkyl) carboxylate and / or bis (epoxycycloalkyl) alkyl carboxylate, and / or wherein the at least one Norbornendicarboxylanhydrid-based Hardener comprises methyl norbornene-2,3-dicarboxylic anhydride. The reaction resin system of any one of claims 2 to 7, wherein the at least one norbornene dicarboxylic anhydride based curing agent comprises a mixture of methyl norbornene-2,3-dicarboxylic anhydride and 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride, wherein the at least one norbornene dicarboxylic anhydride-based curing agent, based on the total weight of the at least one norbornene dicarboxylic anhydride-based curing agent, ≥ 70 wt .-% to ≤ 90 wt .-% methyl norbornene-2,3-dicarboxylanhydrid and ≥ 10 wt .-% bis ≤30% by weight of 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride. Reaction resin system according to one of claims 2 to 8, wherein the amount of the at least one cycloaliphatic epoxy resin to the amount of at least one Norbornendicarboxylanhydrid-based curing agent in a weight ratio of 100: 90 to 100: 130, is, and / or wherein the epoxy resin formulation further comprises at least one accelerator, in particular an imidazole-based accelerator, wherein the amount of the at least one cycloaliphatic epoxy resin to the amount of at least one accelerator in a weight ratio of 100: 0.1 to 100: 3, stands, and / or wherein the amount of the at least one norbornene dicarboxylic anhydride-based curing agent to the amount of at least one accelerator in a weight ratio of 100: 0.1 to 100: 3, in particular wherein the epoxy resin formulation, based on the total weight of the epoxy resin formulation, ≥ 0 wt. % to ≤ 2% by weight of accelerator. A reaction resin system according to any one of claims 3 to 9, wherein the cyanate ester formulation At least one polymeric cyanate ester, - At least one monomeric cyanate ester and At least one polyorganosiloxane, contains. The reaction resin system of claim 10, wherein the amount of the at least one polymeric cyanate ester is from 8: 1 to 12: 1 by weight of the at least one monomeric cyanate ester, and / or wherein the cyanate ester formulation is ≥ 70, based on the total weight of the cyanate ester formulation Wt .-% to ≤ 99 wt .-% of the at least one polymeric cyanate ester comprises, and / or wherein the amount of the at least one monomeric cyanate ester to the amount of at least one polyorganosiloxane in a weight ratio of 1: 1 to 2: 1. Reaction resin system according to claim 10 or 11, wherein the at least one polymeric cyanate ester comprises a polyphenol cyanate, in particular oligo (3-methylene-1,5-phenylcyanoate), and / or wherein the at least one monomeric cyanate ester comprises a bisphenol-based cyanate ester, in particular a bisphenol E-based cyanate ester, and / or wherein the at least one polyorganosiloxane is contained in the form of Polyorganosiloxanteilchen in the reaction resin system, in particular wherein the Polyorganosiloxanteilchen are contained in finely divided form in the at least one cyanate ester. Epoxy resin formulation, in particular for the production of a reaction resin system according to one of claims 1 to 12, comprising - At least one cycloaliphatic epoxy resin and At least one norbornene dicarboxylic anhydride based hardener, wherein the epoxy resin formulation, based on the total weight of the epoxy resin formulation, ≥ 0 wt .-% to ≤ 2 wt .-% of accelerator comprises. Epoxy resin formulation according to claim 13, wherein the at least one norbornene dicarboxylic anhydride based curing agent comprises methyl norbornene-2,3-dicarboxylic anhydride, and / or wherein the at least one cycloaliphatic epoxy resin comprises an epoxycycloalkyl carboxylate, in particular a bis (epoxycycloalkyl) carboxylate and / or bis (epoxycycloalkyl) alkylcarboxylate. The epoxy resin formulation of claim 13 or 14 wherein the at least one norbornene dicarboxylic anhydride based curing agent comprises a mixture of methyl norbornene-2,3-dicarboxylic anhydride and 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride, wherein the at least one a norbornene dicarboxylic anhydride based curing agent, based on the total weight of the at least one norbornene dicarboxylic anhydride based curing agent, ≥ 70 wt .-% to ≤ 90 wt .-% methyl norbornene-2,3-dicarboxylanhydrid and ≥ 10 wt .-% to ≤ 30 Wt% of 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride. An epoxy resin formulation according to any one of claims 13 to 15, wherein the amount of the at least one cycloaliphatic epoxy resin to the amount of at least one Norbornendicarboxylanhydrid-based curing agent in a weight ratio of 100: 90 to 100: 130, is, and / or wherein the amount of the at least one cycloaliphatic epoxy resin to the amount of the at least one accelerator in a weight ratio of 100: 0.1 to 100: 3, stands, and / or wherein the amount of the at least one norbornene dicarboxylic anhydride based curing agent is in the amount of at least one accelerator in a weight ratio of 100: 0.1 to 100: 3. Cyanate ester formulation, in particular for the preparation of a reaction resin system according to one of claims 1 to 12, comprising At least one polymeric cyanate ester, - At least one monomeric cyanate ester and At least one polyorganosiloxane, wherein the amount of the at least one polymeric cyanate ester to the amount of the at least one monomeric cyanate ester in a weight ratio of 8: 1 to 12: 1. The cyanate ester formulation of claim 17, wherein the cyanate ester formulation comprises, based on the total weight of the cyanate ester formulation, ≥ 70% to ≤ 99% by weight of the at least one polymeric cyanate ester and / or wherein the amount of the at least one monomeric cyanate ester is that amount the at least one polyorganosiloxane is in a weight ratio of 1: 1 to 2: 1. Cyanate ester formulation according to claim 17 or 18, wherein the at least one polymeric cyanate ester comprises a polyphenol cyanate, especially oligo (3-methylene-1,5-phenylcyanoate), and / or wherein the at least one monomeric cyanate ester comprises a bisphenol-based cyanate ester, especially a bisphenol E-based cyanate ester , and / or wherein the at least one polyorganosiloxane is contained in the form of Polyorganosiloxanteilchen in the reaction resin system, in particular wherein the Polyorganosiloxanteilchen are contained in finely divided form in the at least one cyanate ester. A process for producing a resin, in particular a cyanate ester resin and / or an epoxy resin, in which a reaction resin system according to any one of claims 1 to 12 and / or an epoxy resin formulation according to any one of claims 13 to 16 and / or a cyanate ester formulation according to any one of claims 17 to 19 is heated to a curing temperature of ≥ 150 ° C.