JP2016130313A - Reactive resin having high conductivity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such a problem that a reaction resin, in particular, a reaction resin containing no filler occasionally has a high coefficient of thermal expansion, for instance, approximately 140 ppm/K when having exceeded a glass transition temperature (Tg) for the application in which the glass transition temperature is exceeded, and the coefficient of thermal expansion is occasionally clearly higher than a coefficient of thermal expansion at a temperature lower than the glass transition temperature, for instance, approximately 65 ppm/K, which may cause a problem.SOLUTION: A reaction resin contains at least one conductive filler, and at least one cyanate ester and/or at least one alicyclic epoxy resin.SELECTED DRAWING: None

Description

  The present invention relates to reactive resin systems, cyanate ester formulations, epoxy resin formulations, and methods for their production, and uses thereof.

  The reaction resin system can be used for joining a joining partner, for example, joining a member and a substrate.

  Patent Document 1 (International Publication No. 2010/036953 (A2)) and Patent Document 2 (US Patent Application Publication No. 5,972,246 (A1)) describe conductive resin compositions.

  Patent Document 3 (German Patent Application Publication No. 102011050675 (A1)), Patent Document 4 (European Patent Application Publication No. 2098571 (A1)) and Patent Document 5 (European Patent Application Publication No. 1854827 (A1)) No.) relates to a resin based on cyanate.

  Patent Document 6 (US Patent Application Publication No. 2009/0298965 (A1)), Patent Document 7 (European Patent Application Publication No. 0307665 (A2)), Patent Document 8 (US Patent Application Publication No. 2011/0315916). (A1) specification) and patent document 9 (U.S. Patent Application Publication No. 2012/0326301 (A1) specification) relate to an epoxy resin composition.

International Publication No. 2010/036953 (A2) US Patent Application Publication No. 5,972,246 (A1) Specification German Patent Application Publication No. 102011050675 (A1) specification European Patent Application No. 2098571 (A1) specification European Patent Application No. 1854827 (A1) Specification US Patent Application Publication No. 2009/0298965 (A1) European Patent Application Publication No. 0307665 (A2) specification US Patent Application Publication No. 2011/0315916 (A1) Specification US Patent Application Publication No. 2012/0326301 (A1) Specification

  However, conventional reactive resin systems generally have a low thermal durability, for example 180 ° C. or below. Furthermore, conventional reactive resin systems generally have only a low glass transition temperature (Tg), for example about 40 ° C. For applications above the glass transition temperature (Tg), the reaction resin system, particularly a reaction resin system that does not include a filler, may have a high coefficient of thermal expansion, for example, about 140 ppm / K, above its glass transition temperature, In particular, the coefficient of thermal expansion can be problematic because it can be clearly higher than the coefficient of thermal expansion below its glass transition temperature, for example about 65 ppm / K.

  The reactive resin system can optionally be used, for example, for electrical contact of the chip.

  The subject of the present invention is a reactive resin system, in particular a reactive resin system for the production of resins. Said reactive resin system may be specifically designed for the production of cyanate ester resins and / or epoxy resins.

  Said reactive resin system may in particular comprise at least one cyanate ester and / or at least one alicyclic epoxy resin. In doing so, the at least one cyanate ester may comprise in particular at least one cyanate ester of a polymer and at least one cyanate ester of a monomer.

  Cyanate esters can represent, for example, monomeric or polymeric compounds having in particular at least two cyanate groups (—O—C≡N). The cyanate esters are preferably capable of crosslinking and curing each other by so-called cyclization trimerization of the three cyanate groups. The cyclization trimerization or curing reaction can in particular be carried out at elevated temperatures, for example at temperatures of 150 ° C. to 280 ° C. By the curing, so-called Duromer can be formed.

  The cyanate ester of the polymer can in particular represent a cyanate ester having at least one repeating unit with a repeat number of at least 2, for example at least 3. Thus, the cyanate ester of the polymer may be an oligomeric cyanate ester.

  Alicyclic epoxy resins in particular have at least one epoxy group, optionally at least two epoxy groups, and at least one cyclic aliphatic group, optionally at least two A compound having a cyclic aliphatic group can be represented. For example, in that case, one (respectively) epoxy group may be bonded to one cyclic aliphatic group.

  In one embodiment, the reactive resin system further contains a curing agent based on at least one polyorganosiloxane and / or at least one norbornene dicarboxyl anhydride.

  A curing agent based on norbornene dicarboxyl anhydride represents in particular a curing agent comprising norbornene dicarboxyl anhydride and / or a norbornene dicarboxyl anhydride derivative, for example methyl-norbornene-2,3-dicarboxyl anhydride. be able to.

  In one particular embodiment, the reactive resin system comprises at least one cyanate ester and, for example, a cyanate ester formulation containing at least one polyorganosiloxane, and / or at least one cycloaliphatic. And an epoxy resin formulation containing a curing agent based on, for example, at least one norbornene dicarboxyl anhydride.

  Accordingly, a further subject of the present invention is also a cyanate ester formulation, in particular at least one cyanate ester, such as a cyanate ester of at least one polymer and / or a cyanate ester of at least one monomer and, for example, at least one. Cyanate ester formulations containing various polyorganosiloxanes, and epoxy resin formulations, in particular at least one cycloaliphatic epoxy resin and, for example, at least one curing agent based on norbornene dicarboxyl anhydride. It is an epoxy resin compound containing. In that case, the cyanate ester formulation or the epoxy resin formulation may be specifically designed for the production of a reactive resin system according to the present invention. In particular, the cyanate ester formulation or the epoxy resin formulation may be configured, for example, as described in connection with the reactive resin system.

  In a further embodiment, the reaction resin system further comprises at least one filler, for example at least one conductive and / or thermally conductive filler, in particular at least one conductive. Contains a filler.

  Such reactive resin systems preferably have high thermal stability or thermal durability and high glass in the cured state, both when fillers are added and even at high filling levels. It can have a transition temperature (Tg) and high mechanical stability and in particular also electrical stability or electrical durability and a relatively low coefficient of thermal expansion over a wide temperature range. In this way, it is possible to reduce thermodynamic stresses on building parts, especially at high temperatures and even when the temperature changes, so that sufficient viscoelastic properties and sufficient mechanical strength can be achieved, for example of vibration. It can be provided for offsetting and thus can be used in a wide working temperature range. Thus, the reaction resin system can be used particularly advantageously at high temperatures and / or even under severe temperature changes.

  Furthermore, such reactive resin systems are preferably capable of binding fillers with a very high degree of filling, in particular fillers with a degree of filling higher than 50% by weight, for example 70% by weight or more.

  By adding a conductive filler, preferably a low electrical resistance, for example an electrical resistance of less than 0.9 mΩ · cm, and a sufficiently high electrical conductivity can be achieved. Preferably, the reactive resin system can thus be configured as conductive (as a whole). Preferably, the reactive resin system, in particular a reactive resin system having a high degree of filling, for example as a lead-free solder replacement material, has no or even low solder destructibility, in particular. And unlike conventional solder materials, it can preferably be used as a solder replacement material with increased reliability. Accordingly, such reactive resin systems can preferably be used for electrical contact and for example for mechanical immobilization.

  Furthermore, the reactive resin system can have a low dielectric constant, preferably in a cured state. The reactive resin system can therefore be used particularly advantageously in high power electronics, for example for electrical contact of high power electronics. Furthermore, resins formed from such reactive resin systems can preferably have high media resistance, which allows their use in a wide field of use.

  In the case of a curing reaction of a reactive resin system, for example, a curing reaction by cyclization trimerization, a volatile substance is hardly eliminated or not eliminated at all. Therefore, an object having particularly few voids or even no voids is more preferable. Can be formed. Therefore, the reactive resin system can also be used particularly preferably as a sealing material.

  Furthermore, it has surprisingly been found that the addition of fillers can reduce the amount of catalyst added in the case of cyanate ester formulations, or even omit the addition of catalyst. Thus, in particular the cyanate ester formulation and optionally the reaction resin system may be catalyst-free.

  In one particular embodiment, the reactive resin system contains at least one conductive filler. For example, the reactive resin system may then be a conductive reactive resin system, or the reactive resin system may be a conductive resin, such as a conductive cyanate ester resin and / or a conductive epoxy. It may be designed for the production of resins.

  In one embodiment, the at least one conductive filler comprises silver and / or silicon and / or carbon nanotubes and / or silicon carbide and / or fullerene and / or copper and / or tin and / or Contains zinc.

  By mixing, preferably processing characteristics and / or functional characteristics can be adjusted. For example, this allows the thermal expansion of the reaction resin system to be matched to the thermal expansion of the silicon chip.

  In a further embodiment, the at least one conductive filler is selected from the group consisting of silver and silicon, carbon nanotubes (Carbo-Nanotubes), silicon carbide, fullerenes, and mixtures thereof. At least one filler 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 mixing silver, optionally silver of various silver types, and other fillers such as silicon powder, carbon nanotubes, silicon carbide or fullerenes, the property profile can preferably be optimized for the application. For example, the thermal expansion coefficient of the reaction resin system can be adjusted to the thermal expansion coefficient of a semiconductor chip, for example, a silicon chip. Furthermore, material costs can preferably be reduced by mixing with such other fillers. For example, by mixing or adding powdered copper, tin and / or zinc, the material cost can be reduced while maintaining sufficient electrical conductivity.

  In particular, the at least one conductive filler may comprise or be formed from silver and silicon. This may be particularly preferable when used as a solder substitute material, particularly when used as a material for a semiconductor chip, for example, a silicon chip.

  Optionally, the at least one conductive filler may be thermally conductive. In this case, the reactive resin system may in particular contain at least one electrically conductive and thermally conductive filler. However, the reactive resin system may further comprise at least one thermally conductive filler.

  A thermally conductive material, for example a thermally conductive filler, represents in particular a material having a specific thermal conductivity, for example a filler, of 2 W / mK or higher, in particular 10 W / mK or higher, for example 20 W / mK or higher. Can do.

  With a thermally conductive filler, it is also possible to achieve a sufficiently high thermal conductivity, for example above 3.5 W / mK. For example, the reactive resin system can thus be configured (as a whole) to be electrically conductive and thermally conductive. Preferably, such a reactive resin system, particularly a reactive resin system with a high degree of filling, can also be used as a heat transfer medium, said reactive resin system being enhanced as a conventional uncrosslinked heat transfer paste Unlike those that expand more intensely at temperature, they can preferably also be used as a means for mechanical immobilization. For example, such reactive resin systems can be used for electrical contact and heat dissipation, for example for mechanical immobilization, for example for mechanical immobilization of high power electronics.

  For example, the at least one thermally conductive filler comprises silicon and / or aluminum oxide and / or silicate, in particular aluminum silicate, such as kayanite, and / or boron nitride and / or carbon nanotubes and / or Silver and / or diamond powder can be included. For example, the at least one thermally conductive filler comprises silicon and / or aluminum oxide and / or silicate, in particular aluminum silicate, such as kayanite, and / or boron nitride and / or carbon nanotubes, In a mixture with silver and / or diamond powder.

  The use of fillers, such as silicon powder, kayanite, boron nitride, carbon nanotubes, and optionally also in mixtures with, for example, silver and / or diamond powder, preferably has a thermal conductivity of, for example, greater than 3.5 W / mK, A crosslinkable material having high mechanical durability or low brittleness and high thermal durability can be realized. By using silicon and / or aluminum oxide and / or silicates, in particular aluminum silicates, such as kayanite and / or boron nitride and / or carbon nanotubes, the material costs can more preferably be reduced.

  Optionally, the at least one thermally conductive filler may be conductive. In this case, the reactive resin system may in particular contain at least one electrically conductive and thermally conductive filler.

  In some cases, the at least one filler, however, is thermally conductive and electrically insulating, for example aluminum oxide and / or boron nitride, and / or the reaction resin system is (in general) heat It may be conductive and electrically insulating. For example, in that case, the reactive resin system may comprise a thermally conductive and (as a whole) electrically insulating filler mixture. For example, in that case, the at least one thermally conductive filler is silicon and / or aluminum oxide and / or silicate, in particular aluminum silicate, such as kayanite, and / or boron nitride and / or carbon nanotubes. Can optionally be included in a mixture with silver and / or diamond powder. In that case, the conductivity is as high as possible of one or more fillers which are themselves thermally conductive and electrically insulating, for example aluminum oxide and / or boron nitride, in particular by themselves being thermally conductive and It can be avoided by using one or more conductive fillers, such as the lowest possible proportion of silver.

  Said at least one filler may be uncoated or coated and may be constituted, for example, in the form of fragments, spheres and / or pieces.

  In a further embodiment, the reaction resin system comprises the at least one filler having a filling degree of 30% by mass to 99% by mass with respect to the total mass of the reaction resin system, In particular, at least one conductive filler, optionally said at least one conductive and / or thermally conductive filler, eg said at least one conductive filler and said at least one thermal conductivity. Includes the sum of all fillers. In particular, the reaction resin system has a filling degree from 45% by weight to 95% by weight, for example from 70% by weight to 80% by weight, based on the total weight of the reaction resin system. Certain fillers, in particular at least one electrically conductive filler, optionally said at least one electrically and / or thermally conductive filler, for example said at least one electrically conductive filler and said at least one Contains the sum of the various thermally conductive fillers. It has proved favorable for achieving high electrical conductivity and / or thermal conductivity. The reactive resin system is thus preferably used as a lead-free solder substitute material and / or as a heat transfer medium, for example for electrical contact and / or for heat dissipation of high power electronics. Can be used.

  The reaction resin system may contain, for example, 1 mass% or more and 70 mass% or less of resin-forming components such as cyanate ester compound and / or epoxy resin compound, based on the total mass of the reaction resin system. It may contain the sum of the cyanate ester formulation and the epoxy resin formulation. For example, the reaction resin system may be, for example, 5% by mass to 55% by mass, for example, 20% by mass to 30% by mass, with respect to the total mass of the reaction resin system, for example, The cyanate ester formulation and / or the epoxy resin formulation may optionally contain the sum of the cyanate ester formulation and the epoxy resin formulation.

  In a further embodiment, the reactive resin system or the cyanate ester formulation comprises at least one cyanate ester of a polymer, at least one monomer cyanate ester, and at least one polyorganosiloxane. To do.

  In a further embodiment, the reaction resin system is based on the total mass of the resin-forming component of the reaction resin system, or the cyanate ester formulation is based on the total mass of the cyanate ester formulation. And at least 70% by mass and up to 99% by mass of the cyanate ester of the at least one polymer.

  With such a high proportion of the cyanate ester of the polymer, preferably the cured cyanate ester resin has a particularly high thermal stability or durability, in particular above 200 ° C., for example above 225 ° C. or even 250 Thermal stability or thermal durability at or above, for example, about 280 ° C. can be achieved. Furthermore, thus preferably a particularly high glass transition temperature (Tg) of the cured cyanate ester resin can be achieved, in particular a glass transition temperature (Tg) of 225 ° C. or higher, for example 250 ° C. or higher, for example about 260 ° C. With such a high glass transition temperature, preferably high mechanical stability and electrical stability or mechanical durability and electrical durability, for example relatively high fracture toughness or low brittleness, over a wide temperature range, in particular Even a high degree of filling can be achieved. Preferably, thus, a low coefficient of thermal expansion can also be achieved over a wide operating temperature range. In this way, it is possible to reduce thermodynamic stresses on building parts, especially at high temperatures and even when the temperature changes, so that sufficient viscoelastic properties and sufficient mechanical strength can be achieved, for example of vibration. It can be provided for offsetting and thus can be used in a wide working temperature range. Furthermore, such reactive resin systems or formulations are preferably capable of binding very high fillers, in particular higher fillers, for example higher than 50%, for example 70% or more. Furthermore, such reactive resin systems or formulations may preferably have a low dielectric constant when cured. Such reactive resin systems or formulations can therefore be used particularly advantageously in high power electronics. Furthermore, resins formed from such reactive resin systems or blends can preferably have a high media resistance, which allows their use in a wide field of use.

  In particular, the reaction resin system is 95% or more by mass with respect to the total mass of the resin-forming component of the reaction resin system, or the cyanate ester compound is 75% by mass or more with respect to the total mass of the cyanate ester compound. The cyanate ester of the at least one polymer may be included up to mass%, for example from 80 mass% to 90 mass%. Thus, preferably the thermal and mechanical stability or thermal and mechanical durability can be further optimized.

  In a further embodiment, the mass ratio of the amount of cyanate ester of the at least one polymer to the amount of cyanate ester of the at least one monomer is 8: 1 to 12: 1. In particular, the mass ratio of the amount of cyanate ester of the at least one polymer to the amount of cyanate ester of the at least one monomer may be 9: 1 to 11: 1, for example about 10: 1. Thus, preferably, thermal stability and mechanical stability or thermal durability and mechanical durability can be further increased.

  In a further embodiment, the mass ratio of the amount of cyanate ester of the at least one monomer to the amount of the at least one polyorganosiloxane is 1: 1 to 2: 1. In particular, the mass ratio of the amount of cyanate ester of the at least one monomer to the amount of the at least one polyorganosiloxane is 1.4: 1 to 1.7: 1, such as 1.5: 1 to 1. 6: 1. Thus, preferably, thermal stability and mechanical stability or thermal durability and mechanical durability can be further increased.

  The reactive resin system is, for example, 0.1% by mass or more based on the total mass of the resin-forming component of the reactive resin system, or the cyanate ester compound is based on the total mass of the cyanate ester compound. Up to 20% by weight or less of the cyanate ester of the at least one monomer may be included. In particular, the reactive resin system is 2% by mass or more and 15% by mass relative to the total mass of the resin-forming component of the reactive resin system, or the cyanate ester compound is based on the total mass of the cyanate ester compound. The cyanate ester of the at least one monomer may be included up to mass%, for example, from 8 mass% to 9 mass%. Thus, preferably the thermal and mechanical stability or thermal and mechanical durability can be further optimized.

  The reactive resin system is, for example, 0.1% by mass or more based on the total mass of the resin-forming component of the reactive resin system, or the cyanate ester compound is based on the total mass of the cyanate ester compound. It may contain up to 20% by weight of said at least one polyorganosiloxane. In particular, the reaction resin system is 10% by mass or more based on the total mass of the resin-forming component of the reaction resin system, or the cyanate ester compound is 1% by mass or more with respect to the total mass of the cyanate ester compound. The at least one polyorganosiloxane may be contained up to mass%, for example from 5 mass% to 6 mass%. Thus, preferably the thermal and mechanical stability or thermal and mechanical durability can be further optimized.

  The amount of cyanate ester of the at least one polymer, the amount of cyanate ester of the at least one monomer, and the amount of the at least one polyorganosiloxane are based on the total mass of the cyanate ester formulation. For example, it may be 100% by mass or less in total. In particular, the amount of cyanate ester of the at least one polymer, the amount of cyanate ester of the at least one monomer, and the amount of the at least one polyorganosiloxane are based on the total mass of the cyanate ester formulation. Thus, the total amount may be 100% by mass.

  For example, the cyanate ester formulation is 70% to 99% by mass, for example 75% to 95% by mass, in particular 80% by mass, based on the total mass of the cyanate ester formulation. Up to 90% by weight of the at least one polymer cyanate ester and 0.1% by weight to 20% by weight, for example 2% to 15% by weight, in particular 8% by weight. Up to 9% by weight of the cyanate ester of the at least one monomer and 0.1% by weight to 20% by weight, for example 1% by weight to 10% by weight, in particular 5% by weight. Up to 6% by weight or less of the at least one polyorganosiloxane may be included, in particular in that case the cyanate ester of the at least one polymer. And the amount of the cyanate ester of the at least one monomer and the amount of the at least one polyorganosiloxane in total is 100% by weight or less, in particular 100% by weight, based on the total weight of the cyanate ester formulation. %.

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

  The cyanate ester of the at least one monomer may be selected, for example, from the group of cyanate esters based on bisphenols and cyanate esters based on novolacs. Examples of cyanate esters based on bisphenol are bisphenol-E-cyanate esters such as 4,4-ethylidene diphenyl cyanate ester, bisphenol-A-cyanate ester, hexafluorobisphenol-A-cyanate ester, tetramethylbisphenol-F- Cyanate ester, bisphenol-M-cyanate ester, bisphenol-C-cyanate ester and cyclopentadienyl bisphenol cyanate ester. Examples of novolak-based cyanate esters are novolak cyanate esters or phenol novolak cyanate esters.

  In a further embodiment, the cyanate ester of the at least one monomer comprises a cyanate ester based on bisphenol or is a cyanate ester based on bisphenol. Bisphenol-based cyanate esters have been found to be preferred to achieve high thermal and mechanical stability or thermal durability and mechanical durability.

  In one particular embodiment of this embodiment, the cyanate ester of the at least one monomer comprises a cyanate ester based on bisphenol-E, in particular bisphenol-E-dicyanate, or bisphenol-E. Base cyanate esters, in particular bisphenol-E-dicyanate. Cyanate esters based on bisphenol-E have been found to be particularly preferred for achieving high thermal and mechanical stability or thermal durability and mechanical durability.

  Said at least one polyorganosiloxane may in particular comprise or be a rubber elastic polymer, for example a rubber elastic polymer having a glass transition temperature in the range from −80 ° C. to −40 ° C. The polyorganosiloxane may be designed for the formation of rubber elastic polymers by cross-linking of rubber elastic polymers having a glass transition temperature in the range, for example, from -80 ° C. to -40 ° C.

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

For example, the at least one polyorganosiloxane comprises a block copolymer which may be derivable from, for example, the general chemical formula: — (R ′ ₂ SiO) _x — (R ″ ₂ SiO) _y — or the block It may be a copolymer. In this case, x and y each represent the number of repetitions and may be 1 or an integer multiple thereof. R ′ and R ″ may then be directly or indirectly bonded to the silicon atom via an oxygen or nitrogen atom and may represent different groups as described for R.

  For example, at least 50% of the groups R or R ′ and / or R ″ may represent a methyl group and / or a phenyl group. Such polyorganosiloxanes are preferably readily available and can achieve good action.

  Optionally, the group R or R ′ and / or R ″ is sufficient for the at least one polyorganosiloxane in the cyanate ester of the at least one monomer and / or the cyanate ester of the at least one polymer. May be selected from the viewpoint of being dispersible. Thus, preferably the addition of a dispersant can be avoided.

  In a further embodiment, the at least one polyorganosiloxane is included in the reaction resin system, in particular in the cyanate ester formulation, in particular in the form of solid or liquid polyorganosiloxane particles. Yes. For example, the polyorganosiloxane particles are in finely dispersed form in the reaction resin system, for example in the cyanate ester formulation or the at least one cyanate ester, in particular in the cyanate ester of the at least one monomer. May be included.

  The polyorganosiloxane particles can have an average diameter of, for example, from 0.01 μm to 50 μm, in particular from 0.05 μm to 20 μm, for example from 0.1 μm to 5 μm. Thus, preferably fracture toughness and impact strength can be improved. The polyorganosiloxane particles may have a unimodal, bimodal, trimodal or multimodal particle size distribution. In particular, the polyorganosiloxane particles may have a wide particle size distribution, for example a particle size distribution over the entire range from 0.1 μm to 5 μm. In that case, a broad particle size distribution may be realized by a broad monomodal distribution, for example by a narrower, bimodal, trimodal or multimodal distribution, respectively.

  As explained in detail in connection with the production method according to the invention, the at least one monomer cyanate ester and the at least one polyorganosiloxane are in particular the at least one monomer cyanate ester, in particular It can be used in the form of a dispersion containing solid or liquid polyorganosiloxane particles comprising at least one polyorganosiloxane. Such a dispersion is preferably excellent in terms of high storage stability. In that case, the at least one polyorganosiloxane may be included in the dispersion, in particular in a crosslinked state to a rubber elastic polymer. The cyanate ester of the at least one monomer can then be contained in the dispersion, in particular essentially uncrosslinked.

  For example, the dispersion is a cyanate of the at least one monomer from 40% by weight to 98% by weight, in particular from 50% by weight to 98% by weight, based on the total weight of the dispersion. Esters may be included. The dispersion contains the at least one polyorganosiloxane, for example, from 2% by weight to 60% by weight, in particular from 2% by weight to 50% by weight, based on the total weight of the dispersion. Good. In particular, the dispersion comprises the at least one polyorganosiloxane of 2% by weight to 10% by weight, for example 4% by weight to 8% by weight, based on the total weight of the dispersion. May be included. Thus, preferably, good fracture mechanics characteristics can be achieved while maintaining a high elastic modulus.

  In some cases, the dispersion may further contain at least one dispersant. By means of a dispersant, preferably the dispersion can be stabilized. Furthermore, this may preferably affect the particle size. Addition of a dispersant may be preferred if optimization in terms of dispersibility of the at least one polyorganosiloxane cannot be achieved or can only be achieved at a cost.

  Said at least one dispersant may comprise or be in particular a compound having an amphiphilic structure. For example, in that case, part of the structure may be compatible with the at least one polyorganosiloxane, and the other part of the structure may be a cyanate ester of the at least one monomer and / or Or it may be affinity for the cyanate ester of said at least one polymer. For example, the at least one dispersant may be an emulsifier or an emulsifier mixture.

  For example, the at least one dispersant may comprise a copolymer consisting of a polyorganosiloxane and a further polymer, such as a polyether, or may be the copolymer. The production of such copolymers is described, for example, by W. Noll in “Chemie and Technologie der Silikone”, Weinheim 1968. The average molecular weight of the at least one dispersant may have a wide range. However, in particular, the at least one dispersant may have an average molecular weight ranging from 300 g / mol to 50,000 g / mol.

  For example, the at least one dispersant may comprise a polyether-polydimethylsiloxane copolymer or may be the copolymer. The proportion of polydimethylsiloxane in the copolymer may be, for example, about 25% by weight relative to the total weight of the copolymer. The polyether of the copolymer may have, for example, ethylene oxide units and / or propylene oxide units. For example, in that case, the ethylene oxide units and propylene oxide units may be present in a ratio of about 40% to 60% by weight. For example, the copolymer may have an average molecular weight in the range of from 10,000 g / mol to 15000 g / mol, for example about 13000 g / mol and / or a viscosity from 2000 mPas to 4000 mPas at 25 ° C. Such copolymers have proved particularly preferred in order to achieve high storage stability.

  For example, the dispersion includes the at least one dispersant in an amount of 0% by mass to 20% by mass, for example, 1% by mass to 15% by mass with respect to the total mass of the dispersion. sell.

  The reactive resin system may in particular be free of polysilazane.

  Optionally, the at least one polyorganosiloxane reacts with the functional groups of the cyanate ester of the at least one monomer and / or the functional group of the cyanate ester of the at least one polymer, especially during the curing reaction. It may have a functional group that can form a chemical bond. For example, the polyorganosiloxane particles may be surface modified with such functional groups. Thus, preferably fracture toughness and impact strength can be improved.

  For example, the groups R or R ′ and / or R ″ of the at least one polyorganosiloxane may be substituted with functional groups.

  Alternatively or additionally, the at least one dispersant and / or the at least one reaction mediator may be combined with the at least one polyorganosiloxane functional group together with the at least one cyanate. A chemical bond is formed, for example, by reacting with the functional group of the cyanate ester of the at least one monomer and / or the functional group of the cyanate ester of the at least one polymer, especially during the curing reaction. The functional group may be provided. For example, the at least one reaction mediator is an organoalkyloxysilane, such as vinyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, aminopropyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, or the like, and The functional group adapted to the at least one polyorganosiloxane and the at least one cyanate ester, for example the cyanate ester of the at least one monomer and / or the cyanate ester of the at least one polymer. An organosilicone copolymer may be included or may be. Suitable organosilicone copolymers may, for example, in principle have the same configuration as the dispersants described above. For example, using organosilicone copolymers that are condensation products of low molecular weight silanol-terminated polydimethylsiloxanes with diglycidyl ethers, hydroxycarboxylic acids or polyesters containing hydroxy and carboxylic acid groups and / or aromatic polyhydroxy compounds can do. Alternatively or in addition, a suitable organosilicone copolymer is a polymethylhydrogensiloxane, a compound having the desired functional group and optionally another olefinic double bond, for example allyl glycidyl. It can be prepared by hydrosilylation with ethers, allyl alcohol, polyethers starting from α-alkene alcohols, allyl methacrylate, 2-hydroxyethyl acrylate and / or maleic anhydride.

  The reaction of the functional group can take place in particular before, at or after (further) further processing of the reaction resin system. For example, the reaction of the functional group can be triggered by an increase in temperature and / or by addition of the at least one reaction mediator and / or by addition of a catalyst.

  The curing of the cyanate ester and / or the reaction of the functional groups can be caused in particular simultaneously and / or by the same measures, for example by increasing the temperature and / or by adding components, for example by adding a catalyst. Curing of the cyanate ester and / or reaction of the functional group can be caused especially after the shaping step.

  In some cases, the reaction resin system may further comprise at least one catalyst. In this way, the curing time and reaction transition can be better controlled in some cases. In some cases, the reaction resin system is a transition metal catalyst, such as cobalt (II) acetylacetonate, such as bisphenol-F-epoxy resin, such as bisphenol-F-epoxy resin obtained by reaction of bisphenol F with epichlorohydrin. What was dissolved in it may be included. For example, in that case, the reaction resin system is 0% by mass or more and 3% by mass or less, for example 0% by mass or more and 1.5% by mass or less, based on the total mass of the reaction resin system. At least one catalyst may be included.

  Surprisingly, it has been found that the catalytic action can be clearly achieved by the addition of at least one filler, so that in the case of cyanate esters, the reaction resin system or the cyanate ester formulation is, in particular, a catalyst. It may be free.

  In a further embodiment, the reactive resin system or the epoxy resin formulation comprises at least one cycloaliphatic epoxy resin and at least one norbornene dicarboxyl anhydride-based curing agent; Containing.

  In this case, a high thermodynamic stability can be achieved by the curing agent based on the at least one norbornene dicarboxyl anhydride, with the at least one alicyclic epoxy resin being used. Preferably, sufficient fracture toughness can be realized. Such a composition preferably gives the cured epoxy resin a particularly high thermal stability or thermal durability, in particular a thermal stability or thermal durability of above 200 ° C., for example about 230 ° C. Can be achieved. Furthermore, preferably, the cured epoxy resin has a particularly high glass transition temperature (Tg), in particular a glass transition temperature (Tg) of 160 ° C. or higher, such as 200 ° C. or higher, such as about 210 ° C., or even 246 ° C. Can be achieved. With such a high glass transition temperature, preferably high mechanical stability or mechanical durability, for example relatively high fracture toughness or low brittleness, can be achieved over a wide temperature range, especially with a high degree of filling. Preferably, thus, a low coefficient of thermal expansion can also be achieved over a wide operating temperature range. In this way, it is possible to reduce thermodynamic stresses on building parts, especially at high temperatures and even when the temperature changes, so that sufficient viscoelastic properties and sufficient mechanical strength can be achieved, for example of vibration. It can be provided for offsetting and thus can be used in a wide working temperature range. Furthermore, such reactive resin systems or formulations are preferably capable of binding very high fillers, in particular higher fillers, for example higher than 50%, for example 70% or more. Furthermore, such reactive resin systems or formulations may preferably have a low dielectric constant when cured. Such reactive resin systems or formulations can therefore be used particularly advantageously in high power electronics. Furthermore, resins formed from such reactive resin systems or blends can preferably have a high media resistance, which allows their use in a wide field of use.

  In a further embodiment, the at least one alicyclic epoxy resin comprises an epoxycycloalkyl-carboxylate, such as epoxycyclohexyl-carboxylate, or an epoxycycloalkyl-carboxylate, such as epoxycyclohexyl. -Carboxylate. For example, the at least one cycloaliphatic epoxy resin may comprise an epoxy cycloalkyl-alkyl carboxylate, such as an epoxy cycloalkyl-methyl carboxylate, or an epoxy cycloalkyl-alkyl carboxylate, such as an epoxy cycloalkyl- It may be methyl carboxylate. In particular, the at least one cycloaliphatic epoxy resin is bis (epoxycycloalkyl) carboxylate and / or bis (epoxycycloalkyl) alkylcarboxylate, such as bis (epoxycyclohexyl) carboxylate and / or bis (epoxy). Cycloalkyl) methyl carboxylates, such as bis (epoxycyclohexyl) methyl carboxylates, such as Daicel Celloxide 2021P or Huntsman Araldit CY 179, or may be. It has proved particularly favorable with regard to achieving the properties already described.

  Curing agents based on the at least one norbornene dicarboxyl anhydride are, for example, methyl-norbornene-2,3-dicarboxyl anhydride (methylnadic acid anhydride), for example 1-methyl-5-norbornene-2, 3-dicarboxylic acid anhydrides, such as HY 906 from Huntsman and / or 8,9,10-trinorborna-5-ene-2,3-dicarboxylic acid anhydride (nadic acid anhydride), or It may be.

  In a further embodiment, the at least one norbornene dicarboxyl anhydride-based curing agent comprises methyl-norbornene-2,3-dicarboxyl anhydride or methyl-norbornene-2 , 3-dicarboxyl anhydride. It has proved particularly favorable with regard to achieving the properties already described.

  In one embodiment of this embodiment, the at least one norbornene dicarboxyl anhydride-based curing agent is methyl-norbornene-2,3-dicarboxyl anhydride (1-methyl- 5-norbornene-2,3-dicarboxylic acid anhydride) and 8,9,10-trinorborna-5-ene-2,3-dicarboxylic acid anhydride or a mixture thereof. Particularly in that case, the at least one norbornene dicarboxyl anhydride-based curing agent is 70% by weight or more based on the total mass of the at least one norbornene dicarboxyl anhydride-based curing agent. Methyl-norbornene-2,3-dicarboxyl anhydride up to 90% by weight and 8,9,10-trinorborna-5-ene-2,3-dicarboxylic acid from 10% by weight to 30% by weight And an anhydride. It has proved particularly favorable with regard to achieving the properties already described.

  In a further embodiment, the mass ratio of the amount of the at least one alicyclic epoxy resin to the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride is 100: 90-100: 130, such as 100: 90 or 100: 100-100: 110 or 100: 120, such as about 100: 100 or 100: 109 or 100: 110. Here, preferably, hygroscopicity can be reduced.

  For example, the reaction resin system is 70% by mass or more with respect to the total mass of the resin-forming component of the reaction resin system, or the epoxy resin compound is 25% by mass or more with respect to the total mass of the epoxy resin compound. Up to mass% or less of the at least one alicyclic epoxy resin may be included. In particular, the reaction resin system is based on the total mass of the resin-forming component of the reaction resin system, or the epoxy resin compound is at least 35% by mass with respect to the total mass of the epoxy resin compound. Up to 50% by weight, for example from 40% to 55% by weight, for example from 47% to 53% by weight, for example about 50% by weight of the at least one alicyclic epoxy resin. May be included. Thus, preferably a balanced property profile can be achieved.

  For example, the reactive resin system is 75% or more by mass with respect to the total mass of the resin-forming component of the reactive resin system, or the epoxy resin compound is 30% by mass or more with respect to the total mass of the epoxy resin compound. Hardeners based on the at least one norbornene dicarboxyl anhydride up to% by weight can be included. In particular, the reactive resin system is based on the total mass of the resin-forming component of the reactive resin system, or the epoxy resin compound is 40% by mass or more and 65% based on the total mass of the epoxy resin compound. Based on at least one norbornene dicarboxyl anhydride up to 50% by weight, for example 45% to 60% by weight, for example 47% to 53% by weight, for example about 50% by weight It may contain a curing agent. Thus, preferably a balanced property profile can be achieved. Optionally, the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride may exceed the amount of the at least one alicyclic epoxy resin.

  In a further embodiment, the reactive resin system or the epoxy resin formulation further comprises at least one accelerator. Said at least one accelerator may for example comprise or be formed from an accelerator based on imidazole, for example imidazole, such as 1-methylimidazole.

  For example, the reactive resin system is 2% or more by mass with respect to the total mass of the resin-forming component of the reactive resin system, or the epoxy resin compound is 0% by mass or more based on the total mass of the epoxy resin compound. It may contain up to at least one accelerator, up to 0.01% by weight and up to 2% by weight, for example up to 2% by weight. In particular, the reaction resin system is 1% by mass or more with respect to the total mass of the resin-forming component of the reaction resin system, or the epoxy resin compound is 0% by mass or more with respect to the total mass of the epoxy resin compound. It may contain up to at least one accelerator, up to 0.01% by weight and up to 1% by weight, for example up to 1% by weight. Thus, preferably, the processing time and the reaction time can be adjusted.

  In particular, the reaction resin system is based on the total mass of the resin-forming component of the reaction resin system, or the epoxy resin compound is based on the total mass of the epoxy resin compound, however, 0% by mass or more. Up to 2% by weight, in particular from 0% by weight to 1% by weight. Thus, preferably an increase in processing time and reaction time can be achieved, for example thereby improving the processing, for example shaping, of the epoxy resin formulation or reaction resin system.

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

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

  In particular, the amount of the at least one alicyclic epoxy resin, the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride, and the amount of the at least one accelerator are It may be 100% by mass or less in total with respect to the total mass of the resin blend. In particular, the amount of the at least one alicyclic epoxy resin, the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride, and the amount of the at least one accelerator are It may be 100% by mass in total with respect to the total mass of the resin blend.

  The reaction resin system is, for example, from 1% by mass to 30% by mass, in particular from 15% by mass to 30% by mass, for example, 20% by mass or more, based on the total mass of the reaction resin system. Up to 25% by weight of the at least one polymer cyanate ester, and / or 0.1% by weight to 5% by weight, in particular 1% to 4% by weight, for example 2% by weight Up to 3% by weight of the cyanate ester of the at least one monomer, and / or 0.1% by weight to 5% by weight, in particular 0.5% to 3% by weight, For example, the at least one polyorganosiloxane of 1% by weight to 2% by weight and / or 1% by weight to 30% by weight, especially 5% by weight to 25% by weight For example, the at least one alicyclic epoxy resin of 10% by mass to 25% by mass and / or 1% by mass to 30% by mass, particularly 5% by mass to 25% by mass. Up to, for example, 10% to 25% by weight of said at least one norbornene dicarboxyl anhydride based curing agent and / or 0% to 1% by weight, for example 0% % To 0.5% by mass or more of the at least one accelerator. In total, in that case, the amount of said at least one cyanate ester (especially the amount of cyanate ester of said at least one polymer and the amount of cyanate ester of said at least one monomer), said at least one polyester The amount of organosiloxane, the amount of the at least one alicyclic epoxy resin, the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride, and the amount of the at least one accelerator are: It may be 1% by mass to 70% by mass, for example 5% by mass to 55% by mass, for example 20% by mass to 30% by mass, based on the total mass of the reaction resin system.

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

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

  In particular, the reactive resin system may further comprise at least one cyanate ester and / or at least one epoxy resin, optionally in a form with improved impact resistance.

  The reactive resin system can be used, for example, in the form of pastes, adhesives, paints or sealants, for example in the form of so-called molding materials.

  The reactive resin system or the cyanate ester formulation or the epoxy resin formulation may be a particularly 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 cyanate ester formulation according to the invention and the epoxy resin formulation according to the invention, there is also an explicit explanation for the process according to the invention and the use according to the invention. As well as the examples.

  A further subject of the present invention is a process for the production of reactive resin systems and / or cyanate ester formulations and / or epoxy resin formulations. In particular, the process may be designed for the production of reaction resin systems according to the invention and / or cyanate ester formulations according to the invention and / or epoxy resin formulations according to the invention.

  In the process, in particular resin-forming components may be mixed. For example, in the process, at least one cyanate ester, such as at least one polymer cyanate ester and / or at least one monomer cyanate ester, and / or at least one cycloaliphatic epoxy resin, and / or Alternatively, at least one polyorganosiloxane and / or at least one norbornene dicarboxyl anhydride-based curing agent may be mixed.

  In particular, it may be admixed with at least one filler, for example at least one conductive and / or thermally conductive filler, in particular at least one conductive filler.

  In one particular embodiment, the cyanate ester of at least one polymer comprises cyanate ester of at least one monomer and in particular solid or liquid polyorganosiloxane particles comprising at least one polyorganosiloxane. The dispersion is mixed with, for example, an emulsion. In that case, the polyorganosiloxane particles may be dispersed in a particularly finely dispersed form, particularly in the cyanate ester of the at least one monomer.

  The dispersion, for example, disperses the at least one polyorganosiloxane, for example in liquid form, first in the cyanate ester of the at least one monomer or in a portion of the cyanate ester of the at least one monomer. Followed by the addition of the at least one polyorganosiloxane crosslinking agent. Optionally, a so-called precatalyzed polyorganosiloxane, ie a polyorganosiloxane that already contains a catalyst, in particular a platinum catalyst, is dispersed in a portion of the cyanate ester of the at least one monomer, followed by the cyanate of the at least one monomer. It is also possible to add a further part of the ester and then finally the crosslinking agent for the at least one polyorganosiloxane. By cross-linking of the already dispersed polyorganosiloxane, dispersed polyorganosiloxane particles can then be formed.

  For example, fine dispersion of a liquid polyorganosiloxane, for example in a liquid cyanate ester, can be achieved, for example, by a known measure and equipment for the production of dispersions or emulsions, for example, with sufficiently high shear in the medium to be dispersed. It can be provided by mechanical devices having an action, such as stirrers, dissolvers, kneaders, roller mills, high-pressure homogenizers, ultrasonic homogenizers and the like. “Ultra Turrax” type dispersion devices can be used, for example, to achieve fine dispersion.

  The particle size distribution of the polyorganosiloxane particles can be determined in advance by the choice of shearing force and, in some cases, the choice of dispersant, during the dispersion process when forming uncrosslinked polyorganosiloxane droplets. Can be controlled by range.

  The average molecular weight of the at least one, for example liquid, for example uncrosslinked polyorganosiloxane, can have a wide range, for example from 800 g / mol to 500,000 g / mol. Thus, preferably, sufficient elasticity can be achieved on the one hand, and fine dispersion of the polyorganosiloxane with acceptable viscosity can be achieved on the other hand. In particular, the at least one, for example liquid, for example uncrosslinked polyorganosiloxane, has an average molecular weight in the range from 1000 g / mol to 100000 g / mol, for example from 1200 g / mol to 30000 g / mol. You can do it.

  The crosslinking of the at least one, for example, liquid polyorganosiloxane to the polyorganosiloxane particles can be performed by, for example, an addition crosslinking method and / or a condensation crosslinking method, particularly an addition crosslinking method.

  For addition cross-linking, the at least one polyorganosiloxane is in particular an olefinic non-hydrogen capable of addition (hydrosilylation reaction) to hydrogen bonded directly to silicon, ie SiH groups, to the SiH groups. It can have a sufficient number of groups with saturated groups. For example, a polydimethylsiloxane having a vinyl end group, for example, the polydimethylsiloxane having 0 to 10% by weight of polymethylhydrogensiloxane added as a crosslinking agent can be used. Said addition crosslinking can be carried out, for example, at room temperature, even at elevated temperatures, for example at temperatures of from 60 ° C. to 140 ° C., optionally in the presence of a catalyst, for example in the presence of a noble metal catalyst. The catalyst may then comprise, for example, at least one element of the platinum group, for example platinum, palladium and / or rhodium. For example, the catalyst may be one dissolved in hexachloroplatinic acid, such as a suitable solvent such as glycol ether and / or isopropanol. A suitable catalyst may be a reaction product of a noble metal chloride with an organic or organosilicon compound containing a vinyl group, or a noble metal that is finely distributed on a suitable support such as activated carbon or aluminum oxide.

  For condensation crosslinking, the at least one polyorganosiloxane is, for example, at least one easily detachable group bonded directly to silicon, such as a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxyimino group, It may have an amine group, an amineoxy group and / or an alkylamide group or hydrogen. In that case, the at least one releasable group may also be included in the at least one polyorganosiloxane and / or in a silane added in particular as a cross-linking agent. For example, the at least one polyorganosiloxane may have hydroxyl end groups, in which case triorganooxysilane or tetraorganooxysilane, such as methyltriacetoxysilane, tetraethoxysilane, methyltris (methylethylketoxyimino) Silane and / or polymethylhydrogensilane are used as crosslinkers. In this case, organic heavy metal salts such as tin, zirconium, lead and / or titanium octanoate, laurate, naphthenate and / or acetate can be used as the catalyst.

  However, in this case, the use of a catalyst is not always necessary, as already explained.

  The three-dimensional cross-linking of the at least one polyorganosiloxane can also be achieved by organic groups R or R ′ and / or R ″ by addition and / or condensation cross-linking of functional groups directly attached to the polyorganosiloxane chain. It can also be achieved by addition cross-linking and / or condensation cross-linking of the functional group bound to.

  Furthermore, the invention relates to reactive resin systems and / or cyanate ester formulations and / or epoxy resin formulations which are produced by such a method. For example, the reaction resin system according to the invention or the cyanate ester formulation or the epoxy resin formulation according to the invention may have been produced by such a method.

  A further subject of the present invention is a process for the production of a resin. In particular, the method may be designed for the production of cyanate ester resins and / or epoxy resins.

  In the above process, in particular the reaction resin system according to the invention and / or the cyanate ester formulation according to the invention and / or the epoxy resin formulation according to the invention and / or the reaction resin system produced according to the invention and / or produced according to the invention. The modified cyanate ester formulation and / or the epoxy resin formulation produced according to the present invention can be heated to a curing temperature of 150 ° C. or higher, in particular 200 ° C. or higher, for example 250 ° C. or higher.

  The invention therefore also relates to resins, in particular cyanate ester resins and / or epoxy resins, which are produced by such a method.

  With regard to further technical features and advantages of the process according to the invention and its products, there are expressly indicated together therewith a reaction resin system according to the invention, a cyanate ester formulation according to the invention, an epoxy resin formulation according to the invention and according to the invention. References to usage as well as examples are referenced.

  Furthermore, the present invention provides 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 produced according to the invention and / or according to the invention. The produced cyanate ester blends and / or the epoxy resin blends produced according to the invention and / or the resins produced according to the invention, in particular cyanate ester resins and / or epoxy resins, in particular of electrical or electronic components, Electrical contact and / or heat dissipation of, for example, electric or electronic components of electric vehicles, for example electric vehicles, and / or renewable energy systems and / or high power electronics, for example transformers and / or converters and / or motors And / or mechanical It relates to the use for the Joka.

  For example, the reaction resin system according to the invention and / or the reaction resin system produced according to the invention and / or the cyanate ester formulation according to the invention and / or the cyanate ester formulation produced according to the invention and / or the epoxy according to the invention Resin blends and / or epoxy resin blends produced according to the invention and / or resins produced according to the invention, in particular cyanate ester resins and / or epoxy resins, can be used, for example, as lead-free solder substitutes . Thus, preferably lead-containing solder materials can be replaced, for example, in high-power electronics, such as transformers, converters and / or motors. For this purpose, the reactive resin system may in particular contain at least one conductive filler. Thus, preferably sufficient electrical contact can be achieved.

  In addition, transformers, converters and motors can exhibit high self-heating. Thus, in some cases, the at least one conductive filler may be thermally conductive.

  Reaction resin systems according to the invention and / or reaction resin systems produced according to the invention and / or cyanate ester formulations according to the invention and / or cyanate ester formulations produced according to the invention and / or epoxy resin formulations according to the invention Products and / or epoxy resin formulations prepared according to the invention and / or resins prepared according to the invention, in particular cyanate ester resins and / or epoxy resins, can be used, for example, as heat transfer media, for example more mechanically. It can also be used as a means for immobilization. For this purpose, the reactive resin system may in particular contain at least one thermally conductive filler. Thus, preferably a high efficiency of heat dissipation can be realized, for example in high power electronics, such as transformers, converters and / or motors. In that case, low conductivity may be desired in some cases. Thus, in some cases, the at least one thermally conductive filler may be electrically insulating.

  With regard to further technical features and advantages of the use according to the invention and its products, explicitly therewith a reactive resin system according to the invention, a cyanate ester formulation according to the invention, an epoxy resin formulation according to the invention and according to the invention Reference is made to the method description as well as the examples.

  Further advantages and preferred embodiments of the subject according to the invention are specifically illustrated by way of example and explained in the following description. In so doing, the examples should be considered as having only the reference signs described and are not intended to limit the invention in any way.

1. Silicone-modified filler-containing cyanate ester The following starting materials were used:
Primaset PT30: polyphenol cyanate; oligo (3-methylene-1,5-phenylene cyanate), Lonza (Switzerland)
Primaset LeCy: 4,4'-ethylidene diphenyl dicyanate, Lonza (Switzerland)
Emulsifier: Polyether-polymethylsiloxane copolymer Polydimethylsiloxane ratio 25% by mass, EO / PO unit ratio 40/60, molecular weight 13000 g / mol, viscosity at 25 ° C. 3000 mPas
Silikon-VM: Premix consisting of 99.5% by weight of α, ω-divinylpolydimethylsiloxane and 0.5% by weight of 1% solution of hexachloroplatinic acid in 2-propanol Crosslinking agent: α, ω-di ( Trimethylsilyl) polymethylhydrogensiloxane Filler:
AG 300-01 from Heraeus (Germany); silver particles, D50 <5 μm
CL 4400FG from Alcoa (Germany); aluminum oxide particles, D50 = 7μm
NO 625-10 from Nabaltec (Germany); aluminum oxide particles, D50 = 2.5 μm

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

1.2 Production of reactive resin systems based on cyanate ester-polyorganosiloxane
To the Primaset PT30, add the silicone modifier and at least one filler. In the range of example CS1, silver particles are used as filler. In the range of Example CS2, a mixture of aluminum oxide particles having an average particle size (D50) of 7 μm and aluminum oxide particles having an average particle size (D50) of 2.5 μm is used as the filler. Their quantitative ratios are shown in Table 1. The material was heated to a curing temperature of 250 ° C.

Table 1: Amount ratio of silicone-modified filler-containing cyanate ester

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

2. Filler-containing alicyclic epoxy resin The following starting materials were used:
Alicyclic epoxy resin: Celloxide 2021P ((3 ′, 4′-epoxycyclohexane) methyl-3,4-epoxycyclohexylcarboxylate) from Daicel
Curing agent: Mixture of 1-methyl-5-norbornene-2,3-dicarboxylic acid anhydride and 8,9,10-trinorborna-5-ene-2,3-dicarboxylic acid anhydride Accelerator: 1-methyl Imidazole From the starting material, the reaction resin system with filler added according to Table 2 was mixed and heated to a curing temperature of 210 ° C.

Table 2: Quantity ratio of alicyclic epoxy resin containing filler

  E1, E2 and E3 preferably exhibit a high glass transition temperature, a high thermal stability and a low coefficient of thermal expansion. E1 showed high conductivity and in particular also thermal conductivity. E2 showed acceptable conductivity and thermal conductivity. E3 had an acceptable thermal conductivity and a high electrical resistance.

[Aspect of the Invention]
1. A reaction resin system,
Said reactive resin system comprising at least one conductive filler, and at least one cyanate ester, and / or at least one alicyclic epoxy resin.
2. 2. The reaction resin system of claim 1, wherein the reaction resin system further comprises a curing agent based on at least one polyorganosiloxane and / or at least one norbornene dicarboxyl anhydride. Resin system.
3. The reaction resin system according to 1 or 2, wherein the reaction resin system is:
-At least one cyanate ester;
-At least one polyorganosiloxane;
A cyanate ester formulation containing: and / or at least one alicyclic epoxy resin;
A curing agent based on at least one norbornene dicarboxyl anhydride;
The reaction resin system comprising an epoxy resin formulation containing
4). The reaction resin system according to any one of 1 to 3, wherein the reaction resin system is 30% by mass to 99% by mass, in particular 45% by mass, based on the total mass of the reaction resin system. The reactive resin system comprising the at least one conductive filler having a filling degree of not less than 95% by mass.
5. 5. The reactive resin system according to any one of 1 to 4, wherein the at least one conductive filler is silver and / or silicon, and / or carbon nanotubes, and / or silicon carbide, and / or Or said reaction resin system comprising fullerene and / or copper and / or tin and / or zinc.
6). The reactive resin system according to any one of 1 to 5, wherein the at least one conductive filler is:
-Silver, and-at least one filler selected from the group consisting of silicon, carbon nanotubes, silicon carbide, fullerene, and mixtures thereof, and / or-a group consisting of copper, tin, zinc, and mixtures thereof At least one filler selected from
Said reactive resin system comprising in particular silver and silicon.
7). The reaction resin system according to any one of 3 to 6, wherein the cyanate ester compound is
At least one cyanate ester of a polymer;
-A cyanate ester of at least one monomer;
-At least one polyorganosiloxane;
Containing said reaction resin system.
8). 7. The reaction resin system according to claim 7, wherein the cyanate ester compound is a cyanate ester of the at least one polymer from 70% by mass to 99% by mass with respect to the total mass of the cyanate ester compound. And / or the mass ratio of the amount of cyanate ester of said at least one polymer to the amount of cyanate ester of said at least one monomer is from 8: 1 to 12: 1 and / or said at least The reaction resin system, wherein the mass ratio of the amount of cyanate ester of one monomer to the amount of the at least one polyorganosiloxane is 1: 1 to 2: 1.
9. Reaction resin system according to 7 or 8, wherein the cyanate ester of the at least one polymer comprises a polyphenol cyanate, in particular oligo (3-methylene-1,5-phenylene cyanate) and / or the at least one The cyanate ester of the species monomer comprises a bisphenol-based cyanate ester, in particular a bisphenol-E-based cyanate ester, and / or the at least one polyorganosiloxane is in the form of polyorganosiloxane particles. In the reaction resin system, in particular, the polyorganosiloxane particles are contained in the at least one cyanate ester in a finely dispersed form.
10. 10. A reaction resin system according to any of 1 to 9, wherein the at least one alicyclic epoxy resin is an epoxycycloalkyl-carboxylate, in particular a bis (epoxycycloalkyl) carboxylate, and / or The reaction wherein the curing agent is a bis (epoxycycloalkyl) alkylcarboxylate and / or the at least one norbornene dicarboxyl anhydride comprises methyl-norbornene-2,3-dicarboxyl anhydride Resin system.
11. 10. The reaction resin system according to claim 10, wherein the curing agent based on at least one norbornene dicarboxyl anhydride is methyl-norbornene-2,3-dicarboxyl anhydride and 8,9,10-trinorborna- A curing agent comprising a mixture of 5-ene-2,3-dicarboxylic anhydride, wherein the at least one norbornene dicarboxyl anhydride is based on the at least one norbornene dicarboxyl anhydride Of methyl-norbornene-2,3-dicarboxyl anhydride up to 70% by weight and up to 90% by weight and 8% up to 30% by weight with respect to the total weight of the curing agent based on , 9,10-trinorborna-5-ene-2,3-dicarboxylic anhydride.
12 A reaction resin system according to any of 2 to 11, wherein the amount of the at least one cycloaliphatic epoxy resin and the amount of curing agent based on the at least one norbornene dicarboxyl anhydride. And / or said epoxy resin formulation further comprises at least one accelerator, in particular an imidazole-based accelerator, wherein said at least The mass ratio of the amount of one alicyclic epoxy resin to the amount of the at least one accelerator is 100: 0.1 to 100: 3 and / or the at least one norbornene dicarboxyl The reaction wherein the mass ratio of the amount of anhydride-based curing agent to the amount of the at least one accelerator is 100: 0.1 to 100: 3 Fat system.
13. A cyanate ester formulation, in particular a cyanate ester formulation for the production of a reaction resin system according to any of 1 to 12, comprising
At least one cyanate ester of a polymer;
-A cyanate ester of at least one monomer;
-At least one polyorganosiloxane;
Wherein the cyanate ester formulation comprises 70% by weight to 99% by weight of the cyanate ester of the at least one polymer, based on the total weight of the cyanate ester formulation, Cyanate ester formulation.
14 13. The cyanate ester formulation of claim 13, wherein the mass ratio of the amount of cyanate ester of the at least one polymer to the amount of cyanate ester of the at least one monomer is 8: 1 to 12: 1. And / or a mass ratio of the amount of cyanate ester of said at least one monomer to the amount of said at least one polyorganosiloxane is from 1: 1 to 2: 1.
15. The cyanate ester formulation according to 13 or 14, wherein the at least one polymer cyanate ester comprises a polyphenol cyanate, in particular an oligo (3-methylene-1,5-phenylene cyanate) and / or said at least The cyanate ester of one monomer comprises a cyanate ester based on bisphenol, in particular a cyanate ester based on bisphenol-E, and / or the at least one polyorganosiloxane is in the form of polyorganosiloxane particles. The cyanate ester blend, which is contained in the reaction resin system, and in particular the polyorganosiloxane particles are contained in the at least one cyanate ester in a finely dispersed form.
16. An epoxy resin formulation, particularly an epoxy resin formulation for the production of a reactive resin system according to any of 1 to 12,
At least one alicyclic epoxy resin;
A curing agent based on at least one norbornene dicarboxyl anhydride;
Wherein the at least one alicyclic epoxy resin comprises an epoxycycloalkyl-carboxylate, in particular a bis (epoxycycloalkyl) carboxylate, and / or a bis (epoxycycloalkyl) alkylcarboxylate. And said epoxy resin formulation wherein said at least one norbornene dicarboxyl anhydride based curing agent comprises methyl-norbornene-2,3-dicarboxyl anhydride.
17. 16. The epoxy resin formulation according to claim 16, wherein the curing agent based on at least one norbornene dicarboxyl anhydride is methyl-norbornene-2,3-dicarboxyl anhydride and 8,9,10-trinorborna. A hardener based on the at least one norbornene dicarboxyl anhydride, wherein the curing agent is based on the at least one norbornene dicarboxyl anhydride. Methyl-norbornene-2,3-dicarboxyl anhydride up to 90% by weight and up to 30% by weight up to 30% by weight with respect to the total weight of the curing agent based on the product. The said epoxy resin compound containing 8,9,10-trinorborna-5-ene-2,3-dicarboxylic anhydride.
18. The epoxy resin formulation according to 16 or 17, wherein the mass ratio of the amount of the at least one alicyclic epoxy resin to the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride. Is 100: 90 to 100: 130 and / or the epoxy resin formulation further comprises at least one accelerator, in particular an imidazole-based accelerator, wherein the at least one accelerator The weight ratio of the amount of alicyclic epoxy resin to the amount of the at least one accelerator is 100: 0.1 to 100: 3, and / or the at least one norbornene dicarboxyl anhydride. A mass ratio of the amount of the curing agent based on the amount of the at least one accelerator is 100: 0.1 to 100: 3. Resin blend.
19. A process for producing a reaction resin system, in particular a reaction resin system according to any of 1 to 12, and / or a cyanate ester compound, in particular a cyanate ester compound according to any of 13 to 15, comprising at least The production method, wherein a cyanate ester of one polymer is mixed with a dispersion containing cyanate ester of at least one monomer and polyorganosiloxane particles composed of at least one polyorganosiloxane.
20. A process for producing a resin, in particular a cyanate ester resin, and / or an epoxy resin, wherein the reaction resin system according to any one of 1 to 12 or 19 and / or the cyanate ester according to any one of 13 to 15 or 19 The said manufacturing method which heats a compound and the epoxy resin compound in any one of 16-18 to the hardening temperature of 150 degreeC or more.

Claims (20)

A reactive resin system containing at least one conductive filler, and at least one cyanate ester, and / or at least one alicyclic epoxy resin.   The reactive resin system according to claim 1, further comprising a curing agent based on at least one polyorganosiloxane and / or at least one norbornene dicarboxyl anhydride. The reaction resin system. The reaction resin system according to claim 1 or 2, wherein the reaction resin system is:
-At least one cyanate ester;
-At least one polyorganosiloxane;
A cyanate ester formulation containing: and / or at least one alicyclic epoxy resin;
A curing agent based on at least one norbornene dicarboxyl anhydride;
The reaction resin system comprising an epoxy resin formulation containing   The reaction resin system according to any one of claims 1 to 3, wherein the reaction resin system is 30% by mass to 99% by mass with respect to the total mass of the reaction resin system. Said reactive resin system comprising in particular said at least one conductive filler with a filling degree from 45% by weight to 95% by weight.   5. The reactive resin system according to claim 1, wherein the at least one conductive filler is silver and / or silicon and / or carbon nanotubes and / or carbonized. Said reactive resin system comprising silicon and / or fullerene and / or copper and / or tin and / or zinc. The reactive resin system according to any one of claims 1 to 5, wherein the at least one conductive filler is:
-Silver, and-at least one filler selected from the group consisting of silicon, carbon nanotubes, silicon carbide, fullerene, and mixtures thereof, and / or-a group consisting of copper, tin, zinc, and mixtures thereof At least one filler selected from
Said reactive resin system comprising in particular silver and silicon. 7. The reactive resin system according to any one of claims 3 to 6, wherein the cyanate ester formulation is
At least one cyanate ester of a polymer;
-A cyanate ester of at least one monomer;
-At least one polyorganosiloxane;
Containing said reaction resin system.   8. The reactive resin system according to claim 7, wherein the cyanate ester formulation is 70% to 99% by mass of the at least one polymer based on the total mass of the cyanate ester formulation. And / or the mass ratio of the amount of cyanate ester of said at least one polymer to the amount of cyanate ester of said at least one monomer is from 8: 1 to 12: 1, and / or The reaction resin system, wherein the mass ratio of the amount of cyanate ester of the at least one monomer to the amount of the at least one polyorganosiloxane is 1: 1 to 2: 1.   9. A reaction resin system according to claim 7 or 8, wherein the cyanate ester of the at least one polymer comprises a polyphenol cyanate, in particular an oligo (3-methylene-1,5-phenylene cyanate) and / or The cyanate ester of the at least one monomer comprises a bisphenol-based cyanate ester, in particular a bisphenol-E-based cyanate ester, and / or the at least one polyorganosiloxane is in the form of polyorganosiloxane particles. In the reaction resin system, particularly, the polyorganosiloxane particles are contained in the at least one cyanate ester in a finely dispersed form.   10. A reactive resin system according to any one of claims 1 to 9, wherein the at least one alicyclic epoxy resin is an epoxycycloalkyl-carboxylate, in particular a bis (epoxycycloalkyl) carboxylate. And / or a curing agent based on bis (epoxycycloalkyl) alkylcarboxylate and / or based on said at least one norbornene dicarboxyl anhydride is methyl-norbornene-2,3-dicarboxyl anhydride. Including the reaction resin system.   11. The reactive resin system according to claim 10, wherein the at least one norbornene dicarboxyl anhydride-based curing agent is methyl-norbornene-2,3-dicarboxyl anhydride and 8,9,10-. A curing agent based on at least one norbornene dicarboxyl anhydride, comprising a mixture of trinorborna-5-ene-2,3-dicarboxylic acid anhydride. Methyl-norbornene-2,3-dicarboxyl anhydride from 70% to 90% by weight and from 10% to 30% by weight, based on the total weight of the curing agent based on anhydride. And 8,9,10-trinorborna-5-ene-2,3-dicarboxylic anhydride.   12. A reactive resin system according to any one of claims 2 to 11, based on the amount of the at least one alicyclic epoxy resin, based on the at least one norbornene dicarboxyl anhydride. The mass ratio to the amount of curing agent is 100: 90 to 100: 130, and / or the epoxy resin formulation further comprises at least one accelerator, in particular an imidazole-based accelerator, Wherein the mass ratio of the amount of the at least one alicyclic epoxy resin to the amount of the at least one accelerator is 100: 0.1 to 100: 3 and / or the at least one type. The mass ratio of the amount of curing agent based on norbornene dicarboxyl anhydride to the amount of the at least one accelerator is 100: 0.1 to 100: 3 The reactive resin system. A cyanate ester formulation, in particular a cyanate ester formulation for the production of a reactive resin system according to any one of claims 1-12,
At least one cyanate ester of a polymer;
-A cyanate ester of at least one monomer;
-At least one polyorganosiloxane;
Wherein the cyanate ester formulation comprises 70% by weight to 99% by weight of the cyanate ester of the at least one polymer, based on the total weight of the cyanate ester formulation, Cyanate ester formulation.   14. The cyanate ester formulation of claim 13, wherein the mass ratio of the amount of cyanate ester of the at least one polymer to the amount of cyanate ester of the at least one monomer is from 8: 1 to 12: 1. And / or the mass ratio of the amount of cyanate ester of said at least one monomer to the amount of said at least one polyorganosiloxane is 1: 1 to 2: 1.   15. Cyanate ester formulation according to claim 13 or 14, wherein the at least one polymeric cyanate ester comprises a polyphenol cyanate, in particular oligo (3-methylene-1,5-phenylene cyanate), and / or The cyanate ester of the at least one monomer comprises a cyanate ester based on bisphenol, in particular a cyanate ester based on bisphenol-E, and / or the at least one polyorganosiloxane comprises polyorganosiloxane particles. The cyanate ester blend, wherein the cyanate ester formulation is included in the reaction resin system in particular, and in particular the polyorganosiloxane particles are included in the at least one cyanate ester in finely dispersed form. An epoxy resin formulation, in particular an epoxy resin formulation for the production of a reactive resin system according to any one of claims 1-12,
At least one alicyclic epoxy resin;
A curing agent based on at least one norbornene dicarboxyl anhydride;
Wherein the at least one alicyclic epoxy resin comprises an epoxycycloalkyl-carboxylate, in particular a bis (epoxycycloalkyl) carboxylate, and / or a bis (epoxycycloalkyl) alkylcarboxylate. And said epoxy resin formulation wherein said at least one norbornene dicarboxyl anhydride based curing agent comprises methyl-norbornene-2,3-dicarboxyl anhydride.   17. The epoxy resin formulation of claim 16, wherein the at least one norbornene dicarboxyl anhydride-based curing agent is methyl-norbornene-2,3-dicarboxyl anhydride and 8,9,10. A mixture of trinorborna-5-ene-2,3-dicarboxylic acid anhydride, wherein the at least one norbornene dicarboxyl anhydride-based curing agent comprises the at least one norbornene dicarboxylic acid anhydride Methyl-norbornene-2,3-dicarboxyl anhydride from 70% by weight to 90% by weight and 10% by weight to 30% by weight relative to the total weight of the curing agent based on carboxyl anhydride Said epoxy resin formulation comprising up to 8,9,10-trinorborna-5-ene-2,3-dicarboxylic anhydride.   18. Epoxy resin formulation according to claim 16 or 17, wherein the amount of the at least one alicyclic epoxy resin is relative to the amount of the curing agent based on the at least one norbornene dicarboxyl anhydride. The mass ratio is from 100: 90 to 100: 130, and / or the epoxy resin formulation further comprises at least one accelerator, in particular an imidazole-based accelerator, wherein the at least 1 The mass ratio of the amount of the alicyclic epoxy resin to the amount of the at least one accelerator is 100: 0.1 to 100: 3 and / or the at least one norbornene dicarboxyl anhydride The mass ratio of the amount of curing agent based on the product to the amount of the at least one accelerator is 100: 0.1 to 100: 3, Epoxy resin formulation.   A reaction resin system, in particular a reaction resin system according to any one of claims 1 to 12, and / or a cyanate ester formulation, in particular a cyanate ester formulation according to any one of claims 13 to 15. A process comprising: mixing a cyanate ester of at least one polymer with a dispersion containing cyanate ester of at least one monomer and polyorganosiloxane particles comprising at least one polyorganosiloxane. Production method.   20. A process for producing a resin, in particular a cyanate ester resin, and / or an epoxy resin, wherein the reaction resin system according to any one of claims 1 to 12 or claim 19 and / or claim 13 to 15 or claim. The said manufacture which heats the cyanate ester compound of any one of Claim 19, and / or the epoxy resin compound of any one of Claims 16-18 to the curing temperature of 150 degreeC or more. Method.