EP3931849A1 - Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique - Google Patents

Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique

Info

Publication number
EP3931849A1
EP3931849A1 EP20714944.4A EP20714944A EP3931849A1 EP 3931849 A1 EP3931849 A1 EP 3931849A1 EP 20714944 A EP20714944 A EP 20714944A EP 3931849 A1 EP3931849 A1 EP 3931849A1
Authority
EP
European Patent Office
Prior art keywords
component
microfiller
fraction
particles
resin according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20714944.4A
Other languages
German (de)
English (en)
Inventor
Karsten ESSER-RANK
Jürgen Huber
Stefan Kern
Matthias ÜBLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3931849A1 publication Critical patent/EP3931849A1/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the invention relates to a novel composition of a casting resin and the use thereof in hot-curing electrical potting, as is used, for example, in the production of insulation, for example for gas-insulated switchgear, electrical components such as transformers, insulators, capacitors, coils and assemblies.
  • the invention relates to a molding material that is obtainable from the casting resin, as well as an electrical insulation which comprises this molding material and the use of such a molding material.
  • Such casting resins are known, in particular as epoxy resins, for potting electrical or electronic components.
  • the live parts In gas-insulated switchgear, the live parts, the so-called main current path, heat up during operation.
  • the heat development results from the loss power of the main current path due to the resistance.
  • the resistance is made up of various components, on the one hand from the line resistances of the current-carrying parts themselves, determined by their cross-section, length and conductive material, on the other hand through the transition resistances at the contact points between different parts of the main current path.
  • non-fixed contact points on moving parts of the current path e.g. the contacts and / or contact systems of the vacuum interrupter - have high resistances, which lead to high local heating, so-called "hot spots".
  • the heating is the limiting factor When designing the switchgear for a certain rated current, as certain temperatures specified by standards must not be exceeded on live components. In order to minimize the heating in the system and to enable the highest possible rated current therefore necessary, on the one hand, to keep the resistance of the main current path as low as possible and, on the other hand, to maximize the heat dissipation through the three types of heat transport - heat radiation, convection and conduction.
  • hardenable cast resin compounds are used for solid insulating molding materials.
  • Casting resins have the advantage that they are usually inexpensive and have a high degree of design flexibility because they can be poured in liquid form, possibly also gelled, and then cured in the mold by suitable measures such as temperature and / or radiation to form a thermoset.
  • Medium and high-fill epoxy resin-based casting resins for hot-curing electrical potting which cure at temperatures in the range from 80 ° C to 200 ° C, usually have a liquid component that is correctly mixed with the reaction stoichiometrically, which includes diepoxy resin, hardener, flexibilizer, accelerator and additives.
  • the diepoxy resins suitable for this are generally known, for example they are diglycidyl ether diepoxy resins, for example bisphenol-A and / or bisphenol-F epoxy resins and / or novolaks.
  • hardener components of the anhydride type such as phthalic anhydride, methyltetrahydrophthalic anhydride, and / or another anhydride derivative and / or any combinations and mixtures of the aforementioned classes of compounds can be used.
  • microfillers with particle diameters in the range of 0.2-1000 ⁇ m are incorporated. These microfillers are often silicon and / or aluminum oxide (s). Since hardened medium and highly filled resin moldings are considered to be brittle, non-ductile materials with only little or no linear elastic properties, a not inconsiderable proportion of flexibilizer of 4-20 parts by weight, based on the filler-free resin matrix, is added to the formulations. to increase the fracture mechanical properties of the material.
  • Casting resins are used for electrical components that are in high voltage / medium voltage from 1 kV.
  • the potting forms, for example, the insulation or at least parts of the insulation.
  • casting resins are state-of-the-art in the electrical industry today and usually take on insulating, supporting or sealing tasks. It is also part of the state of the art that metallic or plastic components are also cast.
  • the casting resins are filled with mineral fillers, e.g. Quartz powder and / or quartz material (crystalline and / or amorphous silicon dioxide, S1O2) or aluminum oxide or electro corundum filled.
  • mineral fillers e.g. Quartz powder and / or quartz material (crystalline and / or amorphous silicon dioxide, S1O2) or aluminum oxide or electro corundum filled.
  • quartz powder and / or quartz material crystalline and / or amorphous silicon dioxide, S1O2
  • aluminum oxide or electro corundum filled e.g. Quartz powder and / or quartz material (crystalline and / or amorphous silicon dioxide, S1O2) or aluminum oxide or electro corundum filled.
  • the hardened molding material also advantageously has high mechanical strength and, at the same time, good fracture mechanical properties. For this purpose, it is particularly advantageous if the tendency of the fillers to sediment in the warm or hot casting resin is low, especially for use in complex preparation and dosing systems and ultimately for the production of high quality, homogeneous molded materials and molded material components.
  • Casting resins are also state of the art, which achieve high thermal conductivity due to an extremely high filler content, for example made of aluminum oxide, with particle sizes of up to 3000 ⁇ m in some cases, but such resins have poor fracture mechanical properties, have high viscosities and are unsuitable, for example, for gap casting. whereby the suitability of the casting resins in question is prevented
  • Molding materials from such casting resins thus contribute a part to dissipate the power loss to the container or other cooler areas of the plant, but the absolute Tar led heat loss is low due to the poor thermal conductivity of the molding material.
  • the commercially available casting resins have too low a thermal conductivity. This is often only 1W / mK or less.
  • the heat exchange in the insulation concerned takes place primarily via convection and / or thermal radiation because the heat dissipation via the thermal conductivity of the insulating resin is too low.
  • micro-filler especially heat-conductive particles
  • the thermal conductivity of a molding material fes can be increased in a targeted manner.
  • the amount of microfiller particles added cannot be varied as desired.
  • the object of the present invention to provide a casting resin of the type mentioned above so that molding materials for insulation are available after curing by the casting of the casting resin in industrially established processing processes, the heat, for example from hot spots, within the Divert and distribute molding materials.
  • the heat loss is distributed within the metal enclosure by conduction and the enclosure acts as a heat sink through the large surface. In this way, the heat is dissipated to the environment with little effort.
  • the casting resins relevant here are characterized by high tensile strength, for example dielectric strengths and / or dielectric strengths of 15 to 25 kV per 100 rpm or 1 mm. Insulations made from them are usually several mm thick so that the required dielectric strengths are achieved.
  • Voluntarily flowing is a state in which the resin divides in a liquid-like manner without pressure differences.
  • the solution to the problem and the subject matter of the present invention is therefore a casting resin comprising at least two components A) and B), where component A) is a liquid component and component B) is a microfiller
  • Component A comprises a resin based on epoxy resin and the associated hardener, hardening catalyst and other additives
  • particles with mean average diameters co in the range from 2 to 400 ⁇ m made of metal oxides, metal nitrides, such as Boron nitride, aluminum oxide and / or silicon dioxide,
  • the microfiller is present in at least three filler fractions of spherically shaped filler particles.
  • the subject matter of the present invention is a molding material obtainable by hardening such a casting resin, as well as an electrical insulation comprising such a molding material.
  • the use of such a casting resin for producing an insulation is the subject of the present invention.
  • Microfiller fractions - especially in combination with spherical polymeric nanoparticles - results in a flowability of the casting resin that allows surprisingly high degrees of filling with thermally conductive fillers while maintaining the processing properties of the casting resin.
  • a casting resin which, at processing temperatures in the lower range of 50 ° C to 90 ° C, more likely 60 ° C to 70 ° C, is a flowing, in particular voluntarily flowing, casting resin compound with a processing viscosity of less than / equal to 20 Pa * s, in particular less than / equal to 17 Pa * s, and very particularly preferably less than / equal to 15 Pa * s, in the shear rate range from 0.1 to 100 1 / s.
  • a zero shear viscosity in the shear rate range of 0.01-0.1 1 / s less than 10 Pa * s is particularly preferred.
  • the dry component B in the casting resin is advantageously in the range from 70% by weight to 98% by weight, in particular in the range from 75% by weight to 95% by weight, in particular in the range from 85% by weight to 90% by weight, based on the processable G understandharzmas se, polymeric nanofillers, resin and hardener components, catalysts and additives.
  • the dry component B in the casting resin is advantageously in the range from 55% by volume to 80% by volume, in particular in the range from 65% by volume to 75% by volume, in particular in the range from 68% by volume to 74% by volume, based on the Processable cast resin masses, including all nanofillers, resin and hardener components, catalysts and additives.
  • the casting resin shows a viscosity and good flowability that are surprisingly low for the person skilled in the art.
  • the microfiller is in a combination of at least three, but preferably four, different filler fractions, i.e. tetramodal, with these filler fractions differing at least in terms of their mean particle diameter d5o, so that there is a "fine" microfill
  • the respective difference is in the range of a power of 10, that is
  • the fine filler fraction F is a medium particle
  • the mean filler fraction M has a mean particle diameter c o in the range 15 ⁇ m to 95 ⁇ m, preferably 30 ⁇ m to 50 ⁇ m, and
  • the coarse filler fraction G has a medium particle
  • diameter c o has in the range 150gm to 500gm and is divided into two coarse fractions Gl and G2 where with
  • - Gl has a mean particle diameter c o in the range from 150 gm to 290 gm, in particular from 180 gm to 260 gm, and
  • - G2 has an average particle diameter c o in the range from 260 gm to 400 gm, in particular from 280 gm to 380 gm.
  • the particles are at least three, but in particular four, filler fractions - including the fraction of the nanoparticles - spherical, that is to say spherical.
  • the material of the spherical fractions F, M and Gl is aluminum oxide and the material of fraction G2, which does not necessarily only have to be spherical, but also - in particular because of its size - can have an unspecific granular, for example pseudo-spherical, shape, hexagonal boron nitride.
  • the respective fractions are preferably monomodal, the filler particles contained therein result in a grain size distribution curve with a maximum c o, e.g. shown in Figure 3, which have no further size, material and / or shape differences.
  • the materials of the filler particles of the individual fractions have the highest possible degree of purity of the material, that is to say only low levels of contamination.
  • the aim is to keep the impurities in the range of less than 2% by weight, in particular preferably less than 1% by weight.
  • a preferred degree of purity is, for example, greater than 97% by weight - preferably higher, of course, e.g. Up to 99.5% by weight of pure aluminum oxide AI2O3.
  • the preferred degree of purity is even higher, for example 98% by weight of pure boron nitride BN, or even up to 99.5% by weight of BN.
  • the invention is a casting resin which heat-cures in the range from 110 ° C. to 140 ° C. to form an electrically insulating molding material. It is particularly desirable here if the hardened molding material, the insulation, has a thermal conductivity of 3 to 5.5 W / mK in the range from 40 ° C to 160 ° C.
  • the casting resin preferably filled with four filler fractions, three of which are spherical, also contains spherical nanoparticles with mean particle diameters co of 30 nm to 200 nm, in particular from 50 nm to 190 nm, preferably from 70 nm to 170 nm and particularly preferably from 80 nm to 140 nm , added.
  • the packing density according to Lee can be increased again to values of over 80% by volume, in particular of over 82% by volume and very preferably of over 83% by volume while maintaining the flowability for processing in the systems mentioned above.
  • the spherical nanoparticles made of soft, polymeric material, optionally with a coating, are preferred.
  • nanoparticles are separated in the cast resin matrix.
  • They are particularly preferably present in a proportion by weight of the total cast resin matrix of less than 5% by weight, preferably of less than 3% by weight and particularly preferably of less than 1% by weight.
  • nano-filler particles act in component B, the micro-filler component, as ball bearings for the finer, medium-sized and also the coarser micro-filler particles and thus increase their flowability.
  • the nanoparticulate filler is particularly preferably in the form of soft nanoparticles, that is to say particles in nano size which - at least in the core - are polymeric and in particular are rubber-like. These particles can also have a rubber-like core with a coating and / or a shell, the shell serving, for example, for better incorporation of the nanoparticles into the resin matrix, but also in particular to ensure that the nanoparticles are as far as possible in the resin matrix present dispersed.
  • the nanoparticles are silanized.
  • Agglomeration of the nanoparticles would be disadvantageous because it neutralizes the effect of the nanoparticles and worsens the function of the nanoparticles within the entire filler fraction.
  • Dispersed nanoparticles exert a kind of ball bearing effect on the larger microfiller particles, making them more flowable and thus reducing the possible filler content of the cast resin compound while still being processed. workability in the systems mentioned at the beginning can be increased.
  • the ductile nanoparticles improve the fracture mechanical property portfolio of the molding material.
  • At least one, but in particular all, filler fractions are composed of spherical, spherical particles.
  • At least three of the four micro-filler fractions have spherical particle shape.
  • the polymer nanoparticles which are preferably also spherical, act like ball bearings.
  • sphericity indicates the ratio of the surface area of a perfect sphere of equal volume compared to the surface area of the particle under consideration.
  • particles have proven to be particularly suitable whose sphericity is in the range of
  • the sphericity can be determined by optical methods, e.g.
  • a suitable measuring device available on the market is, for example, the device: horibaPSA300, see also
  • the proportion of particles in the filler which meet these requirements for sphericity should be as high as possible, in particular it should be above 80%, preferably above 90% and in particular above 95%.
  • the microfiller is in a combination of four particle fractions. It is particularly advantageous in terms of thermal conductivity if the fourth microfiller fraction is a filler fraction with coarse particles.
  • microfiller is preferably present in four fractions, where
  • FIG. 1 a graph of a corresponding grain size distribution is shown, which shows four peaks with a corresponding particle diameter.
  • FIGS. 2 to 5 each show graphs of the individual filler fractions and the particle size distribution of exemplary and preferred filler fractions, which shows
  • FIG. 2 shows an example of a fine filler fraction with c o in the range between 3 pm and 6 pm, in particular in the range between 4 pm and 5 pm,
  • FIG. 3 shows an example of a mean filler fraction with c o in the range between 25 pm to 60 mpi, in particular in the range between 35 pm and 45 pm,
  • FIG. 4 shows an example of a first coarse filler fraction with c o in the range between 180 pm and 290 pm, in particular in the range between 220 pm and 270 pm
  • FIG. 5 shows an example of a second coarse filler fraction with c o in the range between 310 pm and 420 pm, in particular between 320 pm and 370 pm.
  • the mean particle diameter c o was measured in the present case by means of light scattering using a “Malvern Mastersizer 2000” device.
  • fillers with sufficient, better still good or excellent thermal conductivity are used, which form spherical or pseudo-spherical microparticles in powder form.
  • Shown in FIGS. 6 and 7 is a spherical nitride compound, thermally conductive boron nitride, which is used in this exemplary embodiment as spherical hexagonal boron nitride.
  • Other suitable materials are, in addition to nitrides such as boron nitride, which can also be pseudo-spherical, also oxides such as metal oxides, in particular special aluminum oxide, each in different Modifikatio NEN and / or crystal forms.
  • Filler materials such as aluminum nitride, cubic boron nitride (cBN), silicon dioxide, dolomites and / or magnesium oxide, all of the above-mentioned compounds in any desired modifications and any mixtures thereof are also conceivable.
  • a particle is referred to as “pseudospheric” in particular if it has a sphericity Y greater than / equal to 0.87; preferably greater than 0.9; particularly preferably greater than 0.93.
  • the microfiller powders for example the aluminum oxide powder of the three or four filler fractions fine-F-, medium -M- and coarse 1 -Gl - and, if applicable, Coarse 2 -G2 - still treated superficially.
  • the particles can be coated or partially coated, in particular a coating with molecules that carry functional groups similar to the epoxy resin molecules, that is, for example, oxirane groups, is used.
  • a coating that has been found to be suitable is a coating with silane which has oxirane groups, for example 3- (glycidyloxypropyl) trimethoxysilane.
  • silane which has oxirane groups, for example 3- (glycidyloxypropyl) trimethoxysilane.
  • Such a filler with functionalized silane partially surface-coated particles is known to the person skilled in the art as an EST “Epoxy Silane Treatment” variant.
  • the volume fraction of the spherical and / or pseudospheric hexagonal boron nitride powder, coarse fraction G2 is less than 7% by volume, preferably less than 6% by volume and particularly preferably less than 4% by volume, based on the entire filled resin mass, liquid or solid , thus based on the voluntary flowing Cast resin compound and / or the molding material formed therefrom by curing.
  • FIG. 6 shows an SEM image with a resolution of up to 500 ⁇ m of a pure fraction of an example for the second coarse microfiller particle fraction according to the present invention.
  • FIG. 7 shows an SEM image with a resolution of up to 200 ⁇ m, so that only a single spherical boron nitride particle of the coarser fraction is shown.
  • the four-component - tetramodal - filler mixture leads to a particularly good packing total filler fraction with a filler fraction space filling of greater than 65%, in particular greater than 70% and particularly preferably greater than 80%.
  • the total filler fraction space filling is determined by the so-called packing coefficient according to Lee c
  • the spherical aluminum oxides of the three to four microfiller fractions F, M, Gl and G2 can be detected both as individual fractions using SEM images and as a mixture.
  • the filler fractions F, M and Gl are made of aluminum oxide and the coarsest G2 filler fraction is made of boron nitride.
  • the nanoparticles are preferably used as masterbatches which are present dispersed in the resin and are therefore not present on the resin-free SEM images shown in the figures.
  • the dispersing resin which absorbs the at least trimodal, but preferably tetramodal filler fraction, itself only has a volume fraction in the casting resin, i.e. the entire prepolymeric casting resin compound, of preferably 25% by volume to 40% by volume, in particular 27% by volume to 37% % By volume and particularly preferably from 30 to 33% by volume, at 20 ° C to 25 ° C, the latter corresponding to about 10% by weight to 14% by weight.
  • FIGS. 8 to 17 show ESEM recordings which were carried out with a Hitachi, type S-4800 II. They show cryogenic fracture surfaces of a molding material prepared according to an exemplary embodiment of the invention.
  • FIG. 8 shows an overview of the fracture surface in a photograph with a resolution of up to 500 ⁇ m, in which mainly the boron nitride fraction G2 and an aluminum oxide fraction M can be seen.
  • an area is drawn in as a rectangle, which can be seen in enlarged resolution in FIG.
  • FIG. 9 shows the detailed view with a resolution of up to 100 pm of the section drawn in FIG.
  • the boron nitride fraction G2 interface and the aluminum oxide fractions M and F can be seen.
  • FIGS. 10 to 15 show recordings from a resolution of 500 pm down to a resolution of 500 nm.
  • FIG. 10 shows the aluminum oxide fractions M and F and the hardened, detached resin matrix surrounding them in a resolution of up to 500 ⁇ m.
  • FIG. 11 shows the detail from FIG. 10 as drawn, with a resolution of up to 100 pm.
  • FIG. 12 shows a resolution of up to 3 pm, in which only particles of the fine microfiller fractions “F” are completely formed, but the nanoparticles dispersed in the detached resin matrix can already be seen.
  • Figures 13 and 14 show a resolution up to 1pm or 100Onm, the particles being the fine microfiller fraction no longer completely fit into the picture, but the nanoparticles are clearly recognizable.
  • FIG. 15 shows an image with a resolution of up to 500 nm, in which resin and dispersed nanoparticles can be seen.
  • FIG. 16 shows recordings of the same sample but with an alternative camera, a CamScan CS44 SEM.
  • a resolution of approx. 120 ⁇ m the large particles showing the spherical aluminum oxide particles of the middle microfiller fraction M and the small spheres showing the spherical aluminum oxide particles of the fine microfiller fraction F can be seen.
  • the coarse micro-filler fraction G2 can be seen as large particles and the second coarse micro-filler fraction Gl as small particles.
  • FIG. 18 shows the particle size distribution of the residue on ignition of an embodiment of the invention with a component B in the form of a tetramodal microfiller fraction.
  • component B of this exemplary embodiment was freshly reassembled and its particle size distribution profile can be seen in FIG.
  • FIGS. 20, 21 show, analogous to FIGS. 18 and 19, similar images of another embodiment of the invention - FIG. 20 - the incineration residue of a molding material according to this embodiment and FIG. 21 shows the profile image of the dry microfiller component B of the same embodiment for comparison.
  • one embodiment includes
  • the finished molding material was freed from the organic resin and nanoparticle content in a refractory crucible with approx. 5 g molding material as an initial weight, by flaming it with a propane / butane gas flame and then pouring it in. This is referred to as "verification”, and the resin-free residue obtained is referred to as "ignition residue”.
  • This residue was ground up like a dog and a grain size distribution was recorded with 2 min ultrasound treatment (20 pm wavelength) for deagglomeration.
  • the tetramodal microfiller fraction component B was prepared from the individual powders according to Example 3 - see below - and the underlying particle size distribution was determined analogously to the incineration residue. The results are shown in FIGS. 20 and 21.
  • microfiller fractions are preferably mixed in component B in the following proportions:
  • a second coarse fraction “G2” with a weight fraction of 0.1 to 10% by weight, preferably 1 to 5% by weight and in particular preferably 2 to 3% by weight.
  • the weight proportions of the 4 fractions add up to 100% weight proportion of component B.
  • the filler fraction G2 which has the largest particles, for example with an average particle diameter c o in the range from 300 to 350 ⁇ m, comprises a nitride, for example a boron nitride, in either a cubic or hexagonal modification.
  • the filler fraction Gl with an average particle diameter co in the range from 180 pm to 260 pm comprises an oxide, for example an aluminum oxide or a magnesium oxide.
  • the filler fraction M with an average particle diameter co in the range from 30 ⁇ m to 50 ⁇ m, comprises an oxide, for example an aluminum oxide or a magnesium oxide.
  • the filler fraction F with an average particle diameter c o in the range from 2 ⁇ m to 5 ⁇ m, comprises an oxide, for example an aluminum oxide or a magnesium oxide.
  • One or at least two filler fractions preferably comprise separated, sintered web-free, spherical aluminum oxide fillers with a purity greater than 90%, preferably greater than 96% and particularly preferably greater than 98%.
  • The% by volume and / or% by weight mentioned in Examples 1 to 6 below relate - in contrast to those mentioned above - to the pure microfiller, that is to say only to component B of the casting resin.
  • thermal conductivities of 3.5 to 5.5 W / mK in the range of 40 ° C to 160 ° C can be achieved.
  • the examples provide molding materials after the casting resin has cured at approx. 120 ° C to 180 ° C. These molding materials have been optimized for the following characteristic values, which can be clearly determined in accordance with international standards: - Molding material thermal conductivity l from 3.5 to 5.5 W / mK, preferably 3.75-5.25 W / mK, most preferably 4-5 W / mK over a temperature range of 40-140 ° C, measured according to ASTM E 1451,
  • Poisson's ratio v - also known as Poisson's ratio -, at 20-25 ° C from 0.1-0.4, preferably 0.15-0.35, most preferably 0.25-0.3,
  • FIGS. 18 to 21 Material fractions are mapped one after the other before incorporation into the casting resin and after incineration of the resin component of the molding material and particle sizes are measured.
  • the two images of the microfiller particle size distributions to be compared can be seen in FIGS. 18 to 21.
  • the figures to be compared that is, Figures 18 and 19 on the one hand and Figures 20 and 21 on the other hand, show deviations, but these are to be expected to the same extent.
  • the person skilled in the art can determine the particle fractions, their quantitative distribution and, of course, their material in the ashing test, i.e. the residue on ignition. What is striking is the correspondence in the profile, which in case of doubt provides evidence that a tetramodal micro-filler mixture is present with the fractions F, M Gl and G2 presented here for the first time as being particularly suitable for filling cast resin systems.
  • the tetramodality of the unashed and ashed microfiller fractions can be identified with certainty and the comparison of the di-, co- and cbo values allow the microfiller fractions used to be identified.
  • Figures 22 to 31 show SEM images of exemplary microfiller - individual fractions, as well as SEM images of ignition residues of the total microfiller fraction after embedding in the resin matrix, hardening to the molding material and removal of the resin matrix by incineration as possible evidence of the microfiller fractions in the molding material, the solid insulation.
  • FIG. 22 shows a 100-fold enlargement of a non-incinerated aluminum oxide of the microfiller fraction “F”.
  • FIG. 23 shows a 1000-fold enlargement of a non-incinerated aluminum oxide of the microfiller fraction “F”.
  • FIG. 24 shows a 100-fold enlargement of a non-incinerated aluminum oxide of the microfiller fraction “M”.
  • FIG. 25 shows a 1000-fold enlargement of a non-incinerated aluminum oxide of the microfiller fraction “M”.
  • FIG. 26 shows a 100-fold enlargement of a non-incinerated aluminum oxide of the microfiller fraction "Gl”.
  • FIG. 27 shows the 100-fold enlargement of a non-incinerated boron nitride of the microfiller fraction "G2".
  • FIG. 28 shows a 1000-fold enlargement of a non-incinerated boron nitride of the microfiller fraction "G2".
  • FIGS. 29 to 31 show the 20, 100 and 1000 times enlargement of the incinerated residue of a molding material according to an exemplary embodiment of the invention, which had contained the individual fractions as in FIGS. 22 to 28.
  • FIGS. 32 to 44 show ESEM images of the incineration residue of a molding material with a component B, the microfiller according to Example 3.
  • FIG. 32 shows an ESEM recording of the incineration residue of the sample with the scale - that is, image edge length - 1 mm.
  • FIG. 33 shows an enlargement from FIG. 32 with the scale 500mpi.
  • FIG. 34 shows a further enlargement on a scale of 100mpi, here the fractions F, M and G2, the latter in the form of boron nitride platelets which form spherical G2 particles.
  • Figures 36 and 37 show a large enlargement, the scale here is 5gm and 2gm, the fraction F of the incineration residue.
  • FIG. 38 shows on a scale "edge length of the image corresponds to 10 pm", in the present case also referred to as “scale 10 pm", fraction F and detached boron nitride platelets of fraction G2 of the incineration residue.
  • FIG. 39 shows the fractions F, M, Gl and G2 of the incineration residue on a 400 ⁇ m scale.
  • FIG. 40 shows the fractions F, M, on the surface of a G2 particle on a scale of 100 pm.
  • FIG. 41 shows fractions F and M on G2 boron nitride on a 50 ⁇ m scale
  • FIG. 42 shows fractions F and M on G2 boron nitride platelets on a 10 ⁇ m scale.
  • FIG. 43 shows fractions F and M on G2 boron nitride plates on a 20 ⁇ m scale.
  • FIG. 44 shows fraction F on a 10 pm scale.
  • FIGS. 45 to 56 show SEM images of the unashed, native microfiller fractions.
  • FIG. 45 shows the microfiller fractions according to Example 3 before incorporation into the casting resin on a 1 mm scale.
  • FIGS. 46 and 48 show enlargements from FIG. 45 on a scale of 500 pm. The filler fractions F, M, Gl and G2 are visible.
  • FIG. 47 shows a further enlargement to the 100 pm scale, particles of the filler fractions F and M can be seen
  • FIG. 49 shows the unashed filler fractions F, M on Eq.
  • FIG. 50 shows the filler fractions F and M on G2 on the 10 pm scale
  • FIG. 51 shows the filler fraction F on the 5 ⁇ m scale
  • FIG. 52 shows the filler fraction F and M on the 10 pm scale on G2, G2 is in the form of boron nitride flakes.
  • FIG. 53 shows the same view as FIG. 52, but on the scale of 50 pm.
  • FIG. 54 shows the F filler fraction on the G2 surface on a scale of 5 pm.
  • FIG. 55 shows particles of the filler fractions F and M on boron nitride platelets of the G2 filler fraction on a scale of 10 ⁇ m.
  • FIG. 56 shows particles of filler fractions F, M to G2 on a scale of 50 ⁇ m.
  • the fillers suggested here as being preferred are largely insensitive to water compared to aluminum nitride and also do not react with the insulating gas SF 6 or alternative insulating gases.
  • the cast resin enables costs to be reduced, as many internal heat sinks in the switchgear are no longer required due to the cooling with the highly thermally conductive molding materials.
  • the highly thermally conductive molding material also enables the power ratings to be increased and thus provides an enormous competitive advantage.
  • the present invention discloses for the first time a universally applicable casting resin which is very flowable in vacuum casting, for example at 70 ° C. and which, after polymerization, results in dielectrically insulating, highly thermally conductive and crack-insensitive molded materials.
  • the dry, one to be dispersed Fillers are each preferably monomodal in their grain size distribution and particularly preferably spherical in shape.
  • the tetramodality of the microfillers used, with the average particle sizes graded in powers of 10 leads to an excellent packing density and shows surprisingly good processability and flow behavior at the highest levels of filling up to 95% by weight, in particular up to 90% by weight, equivalent in proportions by volume of 65 vol% to 72 vol%.
  • the invention makes it possible for the first time to use such highly filled and thus highly thermally conductive casting resins in the above-mentioned systems for automatic pressure gelling process -ADG- and / or in a (vacuum) circulating casting system -UGA-.

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Abstract

L'invention concerne une nouvelle combinaison d'une résine de coulée et son utilisation dans l'encapsulation électrique thermodurcissable, comme elle est utilisée, par exemple, dans la fabrication d'isolants, par exemple, pour les appareillages de commutation isolés au gaz, les composants électriques tels que les transformateurs, les isolateurs, les condensateurs, les bobines et les assemblages. L'invention concerne en outre un matériau de moulage qui peut être obtenu à partir de la résine de coulée, ainsi qu'une isolation électrique comprenant ce matériau de moulage et l'utilisation d'un tel matériau de moulage. En particulier, la tétramodalité des microcharges utilisées, dont la taille moyenne des particules est graduée en puissance de 10, conduit à une excellente densité d'implantation et montre une étonnante facilité de traitement et un bon comportement à l'écoulement aux plus hauts niveaux de remplissage, jusqu'à 95% en poids. L'invention permet pour la première fois d'utiliser ces résines de coulée hautement chargées et donc hautement thermoconductrices dans les installations mentionnées ci-dessus pour la gélification automatique sous pression (ADG) et/ou dans une installation de coulée à circulation (sous vide) (UGA).
EP20714944.4A 2019-03-27 2020-03-18 Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique Pending EP3931849A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019204191.4A DE102019204191A1 (de) 2019-03-27 2019-03-27 Gießharz, Formstoff daraus, Verwendung dazu und eine elektrische Isolierung
PCT/EP2020/057499 WO2020193323A1 (fr) 2019-03-27 2020-03-18 Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique

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EP3931849A1 true EP3931849A1 (fr) 2022-01-05

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EP (1) EP3931849A1 (fr)
CN (1) CN113906524A (fr)
DE (1) DE102019204191A1 (fr)
WO (1) WO2020193323A1 (fr)

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Publication number Priority date Publication date Assignee Title
RU2194323C2 (ru) * 2001-01-12 2002-12-10 Открытое акционерное общество "Всероссийский научно-исследовательский и проектно-конструкторский институт электровозостроения" Электроизоляционная теплопроводящая композиция
WO2004065469A1 (fr) * 2003-01-23 2004-08-05 Siemens Aktiengesellschaft Systeme de resine de coulee fortement charge
JP4112396B2 (ja) * 2003-02-13 2008-07-02 電気化学工業株式会社 樹脂用充填材および用途
DE10345312A1 (de) * 2003-09-30 2005-04-14 Robert Bosch Gmbh Härtbares Reaktionsharzsystem
DE502004007114D1 (de) * 2003-09-29 2008-06-26 Bosch Gmbh Robert Härtbares Reaktionsharzsystem
DE10345139A1 (de) * 2003-09-29 2005-04-21 Bosch Gmbh Robert Härtbares Reaktionsharzsystem
JP4525139B2 (ja) * 2004-03-31 2010-08-18 住友ベークライト株式会社 半導体封止用エポキシ樹脂組成物の製造方法。
JP2008075069A (ja) * 2006-08-23 2008-04-03 Toshiba Corp 注型樹脂組成物およびそれを用いた絶縁材料、絶縁構造体
DE102008030904A1 (de) * 2008-06-30 2009-12-31 Siemens Aktiengesellschaft Verbundmaterial mit Nano-Pulver und Verwendung des Verbundmaterials
DE102010015398A1 (de) * 2010-04-19 2011-10-20 Siemens Aktiengesellschaft Isolationsverbundmaterial zur elektrischen Isolation, Verfahren zur Herstellung und Verwendung desselben
DE102013205117A1 (de) * 2013-03-22 2014-09-25 Siemens Aktiengesellschaft Vergussmasse, Verwendung der Vergussmasse, thermisch gehärteter Komposit erhältlich aus der Vergussmasse und elektrische Maschine mit der Vergussmasse
US9670377B2 (en) * 2014-03-04 2017-06-06 Namics Corporation Underfill composition for encapsulating a bond line
DE102016205386A1 (de) * 2016-03-31 2017-10-05 Robert Bosch Gmbh Härtbare Epoxidharz-Gießmasse

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WO2020193323A1 (fr) 2020-10-01
DE102019204191A1 (de) 2020-10-01

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