WO2018139642A1 - Matière et stratifié à base de résine - Google Patents

Matière et stratifié à base de résine Download PDF

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Publication number
WO2018139642A1
WO2018139642A1 PCT/JP2018/002719 JP2018002719W WO2018139642A1 WO 2018139642 A1 WO2018139642 A1 WO 2018139642A1 JP 2018002719 W JP2018002719 W JP 2018002719W WO 2018139642 A1 WO2018139642 A1 WO 2018139642A1
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boron nitride
aggregated particles
nitride aggregated
particles
less
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PCT/JP2018/002719
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English (en)
Japanese (ja)
Inventor
悠子 川原
圭吾 大鷲
剛児 足羽
匡隆 杉本
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積水化学工業株式会社
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Priority to JP2018506235A priority Critical patent/JPWO2018139642A1/ja
Publication of WO2018139642A1 publication Critical patent/WO2018139642A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks

Definitions

  • the present invention relates to a resin material containing boron nitride aggregated particles and a binder resin. Moreover, this invention relates to the laminated body using the said resin material.
  • a ceramic substrate having high thermal conductivity as a heat dissipation substrate for mounting a power semiconductor device or the like.
  • a ceramic substrate include an alumina substrate and an aluminum nitride substrate.
  • the means using the ceramic substrate has a problem that it is difficult to make a multilayer, workability is poor, and cost is very high. Furthermore, since the difference in coefficient of linear expansion between the ceramic substrate and the copper circuit is large, there is also a problem that the copper circuit is easily peeled off during the cooling and heating cycle.
  • a resin composition using boron nitride having a low coefficient of linear expansion, particularly hexagonal boron nitride has attracted attention as a heat dissipation material.
  • the crystal structure of hexagonal boron nitride is a layered structure of hexagonal network similar to graphite, and the particle shape of hexagonal boron nitride is scaly. For this reason, it is known that hexagonal boron nitride has a property in which the thermal conductivity in the plane direction is higher than the thermal conductivity in the thickness direction and the thermal conductivity is anisotropic.
  • boron nitride agglomerated particles in which the primary particles of hexagonal boron nitride are agglomerated as a method of reducing the thermal conductivity anisotropy of hexagonal boron nitride and improving the thermal conductivity in the thickness direction. It has been proposed to use Patent Documents 1 to 3 below disclose resin compositions using boron nitride aggregated particles.
  • Patent Document 1 discloses a thermosetting resin composition containing an inorganic filler in a thermosetting resin.
  • the inorganic filler includes a secondary aggregate (A) composed of primary particles of boron nitride having an average major axis of 8 ⁇ m or less, and a secondary aggregate composed of primary particles of boron nitride having an average major axis of more than 8 ⁇ m and 20 ⁇ m or less.
  • the next aggregate (B) is contained in a volume ratio of 40:60 to 98: 2. Content of the said inorganic filler is 40 volume% or more and 80 volume% or less.
  • Patent Document 2 discloses a curable heat radiation composition comprising two types of fillers having different compressive fracture strengths (except that the above two types of fillers are the same substance) and a curable resin (C). Things are disclosed.
  • the compression fracture strength ratio compression fracture strength of filler (A) having a high compression fracture strength / compression fracture strength of filler (B) having a small compression fracture strength
  • the filler (B) is hexagonal boron nitride aggregate particles.
  • Patent Document 3 discloses a thermosetting resin composition containing a thermosetting resin and an inorganic filler.
  • the inorganic filler is formed of secondary particles (A) formed from primary particles of boron nitride having an aspect ratio of 10 or more and 20 or less, and primary particles of boron nitride having an aspect ratio of 2 or more and 9 or less.
  • Secondary particles (B) are formed of secondary particles (A) formed from primary particles of boron nitride having an aspect ratio of 10 or more and 20 or less, and primary particles of boron nitride having an aspect ratio of 2 or more and 9 or less.
  • the area of the end face where the boron nitride aggregated particles constituting the boron nitride aggregated particles are relatively large may be small.
  • the adhesiveness between the boron nitride aggregated particles and the curable compound may be reduced, or the adhesiveness between the curable composition and the adherend may be reduced.
  • An object of the present invention is to provide a resin material that can effectively enhance insulation, can effectively suppress variations in dielectric breakdown strength, and can effectively enhance adhesion, and the resin material It is providing the laminated body using this.
  • the first boron nitride aggregated particles, the second boron nitride aggregated particles, and a binder resin the pore diameter of the first boron nitride aggregated particles exceeds 0 ⁇ m,
  • the specific surface area in the pores of 5 ⁇ m or less is 1.3 m 2 / g or more, and the specific surface area of the second boron nitride aggregated particles in the pores having a pore diameter of more than 0 ⁇ m and 5 ⁇ m or less is 1
  • the resin material is less than .3 m 2 / g and the porosity of the second aggregated boron nitride particles is 35% or more.
  • a particle diameter of the first boron nitride aggregated particles exceeds 40 ⁇ m, and an average major axis of the primary particles constituting the first boron nitride aggregated particles is 2 ⁇ m or more. , And the average major axis of the primary particles constituting the second boron nitride aggregated particles is 8 ⁇ m or less.
  • a total content of the first boron nitride aggregated particles and the second boron nitride aggregated particles in 100 volume% of the resin material is 20 volume% or more, 80% by volume or less.
  • the resin material is a resin sheet.
  • a heat conductor an insulating layer laminated on one surface of the heat conductor, and a conductive layer laminated on the surface of the insulating layer opposite to the heat conductor.
  • a laminate is provided in which the material of the insulating layer is the resin material described above.
  • the resin material according to the present invention includes first boron nitride aggregated particles, second boron nitride aggregated particles, and a binder resin.
  • the specific surface area of the first boron nitride aggregated particles in the pores having a pore diameter of more than 0 ⁇ m and 5 ⁇ m or less is 1.3 m 2 / g or more.
  • the specific surface area of the second boron nitride aggregated particles in the pores having a pore diameter of more than 0 ⁇ m and 5 ⁇ m or less is less than 1.3 m 2 / g.
  • the porosity of the second boron nitride aggregated particles is 35% or more.
  • FIG. 1 is a cross-sectional view schematically showing a resin sheet according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a laminate obtained using the resin material according to one embodiment of the present invention.
  • FIG. 3 is a diagram showing an example of the relationship between the pore volume difference and the pore diameter in the present invention.
  • FIG. 4 is a diagram showing an example of the difference between the first boron nitride aggregated particles and the second boron nitride aggregated particles in the present invention.
  • the resin material according to the present invention includes first boron nitride aggregated particles, second boron nitride aggregated particles, and a binder resin.
  • the specific surface area of the first boron nitride aggregated particles in the pores having a pore diameter of more than 0 ⁇ m and 5 ⁇ m or less is 1.3 m 2 / g or more.
  • the porosity of the second boron nitride aggregated particles is 35% or more.
  • the second boron nitride aggregated particles since the specific surface area of the second boron nitride aggregated particles is relatively small and the porosity of the second boron nitride aggregated particles is relatively large, the second boron nitride aggregated There are few contacts between the primary particles constituting the particles (see FIG. 4B). For this reason, when compression force such as a press is applied, the second boron nitride aggregated particles are preferentially deformed or collapsed before the first boron nitride aggregated particles are deformed or collapsed. As a result, the second boron nitride aggregated particles that are appropriately deformed or collapsed can fill voids that exist between the first boron nitride aggregated particles that are not excessively deformed or collapsed. Can be enhanced.
  • first boron nitride agglomerated particles primary particles are close to each other, and primary particles having a large aspect ratio may be entangled. Therefore, even if a compression force such as a press is applied, movement of a large number of primary particles is required, and thus the first boron nitride aggregated particles are difficult to collapse even if they are deformed (FIG. 4A )reference). When a compressive force is applied, the first boron nitride aggregated particles are difficult to collapse, and the second boron nitride aggregated particles are easily deformed or collapsed.
  • the first boron nitride aggregated particles are not excessively collapsed by pressing or the like, and the second boron nitride aggregated particles are appropriately deformed or collapsed.
  • the press pressure at which the second boron nitride aggregated particles are deformed or collapsed is lower than the press pressure at which the first boron nitride aggregated particles are deformed or collapsed.
  • the first boron nitride aggregated particles are hardly deformed or collapsed by the press, and the surface direction and thickness are reduced.
  • the thermal conductivity in the vertical direction can be improved, voids remain between the first boron nitride aggregated particles, and the insulating properties deteriorate.
  • the pressing is performed so as to eliminate the voids, even the first boron nitride aggregated particles cannot maintain their form, and the thermal conductivity in the thickness direction decreases.
  • the thermal conductivity in the thickness direction may decrease.
  • the resin material according to the present invention uses two types of boron nitride agglomerated particles having different specific surface areas, and the first boron nitride agglomerated particles having a large specific surface area have many contacts between the primary particles, the specific surface area is small, and The second boron nitride aggregated particles having a large porosity have few contacts between primary particles. For this reason, when a compression force is applied by a press or the like, the second boron nitride aggregated particles are appropriately deformed or collapsed around the first boron nitride aggregated particles. Moreover, the 2nd boron nitride aggregated particle after compression can fill the space
  • the specific surface area of the second boron nitride aggregated particles is relatively small, generation of voids close to the primary particles can be suppressed. Further, the compressed second boron nitride aggregated particles and the primary particles constituting the second boron nitride aggregated particles can fill the gaps between the first boron nitride aggregated particles without any gaps. As a result, partial discharge (internal discharge) generated in the gap can be suppressed, and variation in dielectric breakdown strength can be effectively suppressed. Moreover, in the resin material which concerns on this invention, since the space
  • the aspect ratio of the primary particles constituting the second boron nitride aggregated particles is also relatively small.
  • the area of the end surface of the primary particles constituting the boron aggregated particles is large.
  • Functional groups such as hydroxyl groups and amino groups are present on the end face, and the amount of functional groups such as hydroxyl groups and amino groups can be increased in the second boron nitride aggregated particles.
  • the primary particles constituting the second boron nitride aggregated particles and the second boron nitride aggregated particles can be bonded to the binder resin, the adherend, and the like via the functional group. As a result, the adhesiveness between the boron nitride aggregated particles and the binder resin and the adhesiveness between the boron nitride aggregated particles and the adherend can be effectively increased.
  • the use of the first boron nitride aggregated particles and the second boron nitride aggregated particles satisfying the relationship between the specific specific surface area and the specific porosity greatly contributes.
  • the specific surface area of the first boron nitride aggregated particles is 1.3 m 2 / g or more. From the viewpoint of further effectively increasing the insulating property, the specific surface area of the first boron nitride aggregated particles is preferably 1.8 m 2 / g or more, more preferably 2.5 m 2 / g or more. The upper limit of the specific surface area of the first boron nitride aggregated particles is not particularly limited. The specific surface area of the first boron nitride aggregated particles may be 15 m 2 / g or less.
  • the specific surface area of the second boron nitride aggregated particles is less than 1.3 m 2 / g. From the viewpoint of more effectively increasing the insulation, the specific surface area of the second boron nitride aggregated particles is preferably 1 m 2 / g or less, more preferably 0.75 m 2 / g or less. The lower limit of the specific surface area of the second boron nitride aggregated particles is not particularly limited. The specific surface area of the second boron nitride aggregated particles may be 0.1 m 2 / g or more.
  • the pore size distribution on the volume basis of the first boron nitride aggregated particles and the second boron nitride aggregated particles can be measured as follows.
  • a mercury porosimeter “pore master 60” manufactured by QUANTACHROME the cumulative amount of mercury intrusion is measured against the pressure applied by the mercury intrusion method. From the obtained data, a distribution curve indicating the pore volume per unit section of the pore diameter is obtained.
  • the specific surface area of the first boron nitride aggregated particles and the second boron nitride aggregated particles can be calculated. Specifically, using the pore diameter (d ( ⁇ m)) obtained by measurement and the pore volume difference ( ⁇ V (cc / g)), the specific surface area ( ⁇ S ( m 2 / g)) can be calculated.
  • the void is regarded as a columnar shape, and the bottom area is not considered. In the case where the above measuring method is used, the effect of the present invention is exhibited.
  • the pore volume difference in the boron nitride agglomerated particles used in the present invention, the pore volume approaches 0 once in the vicinity of 5 ⁇ m. This is considered to indicate the pores inside the particles. Therefore, the specific surface area is calculated by adding ⁇ S in pores having a pore diameter exceeding 0 ⁇ m and not more than 5 ⁇ m.
  • FIG. 3 is a schematic diagram showing an example. Further, it is considered that there are closed pores without mercury intrusion, but the amount is small, and the effect of the present invention can be sufficiently achieved even by defining without considering closed pores.
  • the specific surface areas of the first boron nitride aggregated particles and the second boron nitride aggregated particles are calculated by averaging five or more measurement results of the specific surface area obtained from the measurement results of the pore size distribution. It is preferable.
  • the porosity of the first boron nitride aggregated particles is preferably 10% or more, more preferably 14%. Or more, preferably 75% or less, more preferably 70% or less.
  • the porosity of the second boron nitride aggregated particles is 35% or more. From the viewpoint of more effectively increasing the insulating property and from the viewpoint of further effectively increasing the thermal conductivity, the porosity of the second boron nitride aggregated particles is preferably 37% or more, more preferably 39. % Or more, preferably 60% or less, more preferably 50% or less.
  • the porosity of the first boron nitride aggregated particles and the second boron nitride aggregated particles can be measured as follows. Note that the porosity includes a portion of the boron nitride aggregate particles that is filled with a binder resin.
  • the pore volume distribution was measured by the mercury intrusion method using a mercury porosimeter “pore master 60” manufactured by QUANTACHROME. Is calculated based on the value of the voids in the aggregated particles. Further, in the relationship between the pore volume difference and the pore diameter (see FIG. 3), in the boron nitride agglomerated particles used in the present invention, the pore volume once approaches 0 at around 5 ⁇ m, so that the pore diameter of 5 ⁇ m or less is nitrided. It is considered that the pores inside the boron aggregated particles are shown.
  • the sum of the volumes of pores having a pore diameter exceeding 0 ⁇ m and 5 ⁇ m or less is used as a reference for calculating the porosity.
  • pore diameters exceeding 5 ⁇ m are considered to indicate pores between boron nitride aggregated particles. This is consistent with the cross-sectional data of the boron nitride aggregate particles.
  • the porosity may be measured using boron nitride aggregated particles before blending with the resin material, or may be measured using boron nitride aggregated particles recovered by removing the binder resin from the resin material.
  • Examples of the method for removing the binder resin from the resin material include a method in which the resin material is heat-treated at a high temperature of 600 ° C. for 5 hours.
  • the method for removing the binder resin from the resin material may be the above-described method or other methods.
  • the particle diameter of the first boron nitride aggregated particles is preferably more than 40 ⁇ m, more preferably 50 ⁇ m. More, preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the particle diameter of the second boron nitride aggregated particles is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more. Yes, preferably 70 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the particle diameters of the first boron nitride aggregated particles and the second boron nitride aggregated particles are preferably average particle diameters obtained by averaging the particle diameters on a volume basis.
  • the particle diameters of the first boron nitride aggregated particles and the second boron nitride aggregated particles can be measured using a “laser diffraction particle size distribution analyzer” manufactured by Horiba, Ltd.
  • the particle diameters of the first boron nitride aggregated particles and the second boron nitride aggregated particles are obtained by sampling 3 g of each boron nitride aggregated particle, and averaging the particle diameter of each boron nitride aggregated particle contained therein.
  • the particle diameter (d50) of the boron nitride aggregated particles when the cumulative volume is 50% is the average particle size. It is preferable to employ the diameter.
  • the aspect ratio of the first boron nitride agglomerated particles is preferably 3 or less, more preferably 2 or less, from the viewpoint of more effectively increasing the insulation and further effectively increasing the thermal conductivity. is there.
  • the lower limit of the aspect ratio of the first boron nitride aggregated particles is not particularly limited.
  • the aspect ratio of the first boron nitride aggregated particle may be 1 or more.
  • the aspect ratio of the second boron nitride agglomerated particles is preferably 3 or less, more preferably 2 or less, from the viewpoint of more effectively increasing the insulation and further effectively increasing the thermal conductivity. is there.
  • the lower limit of the aspect ratio of the second boron nitride aggregated particles is not particularly limited.
  • the second boron nitride aggregate particle may have an aspect ratio of 1 or more.
  • the aspect ratio of the first boron nitride aggregated particles and the second boron nitride aggregated particles indicates a major axis / minor axis.
  • the aspect ratio of the first boron nitride aggregated particles and the second boron nitride aggregated particles is preferably an average aspect ratio obtained by averaging the aspect ratios of the plurality of boron nitride aggregated particles.
  • the average aspect ratio of the first boron nitride aggregated particles and the second boron nitride aggregated particles was determined by observing 50 arbitrarily selected boron nitride aggregated particles with an electron microscope or an optical microscope. It is calculated
  • the thermal conductivity of the first boron nitride aggregated particles is preferably 5 W / m ⁇ K or more, more preferably 10 W / m ⁇ K or more.
  • the upper limit of the thermal conductivity of the first boron nitride aggregated particles is not particularly limited.
  • the first boron nitride aggregated particles may have a thermal conductivity of 1000 W / m ⁇ K or less.
  • the thermal conductivity of the second boron nitride aggregated particles is preferably 5 W / m ⁇ K or more, more preferably 10 W / m ⁇ K or more.
  • the upper limit of the thermal conductivity of the second boron nitride aggregated particles is not particularly limited.
  • the second boron nitride aggregated particles may have a thermal conductivity of 1000 W / m ⁇ K or less.
  • the first boron nitride aggregated particles and the second boron nitride aggregated particles are contained in 100% by volume of the resin material. Is preferably 20% by volume or more, more preferably 45% by volume or more, preferably 80% by volume or less, more preferably 70% by volume or less.
  • the production method of the first boron nitride aggregated particles and the second boron nitride aggregated particles is not particularly limited, and examples thereof include a spray drying method and a fluidized bed granulation method.
  • the method for producing the first boron nitride aggregated particles and the second boron nitride aggregated particles is preferably a spray drying (also called spray drying) method.
  • the spray drying method can be classified into a two-fluid nozzle method, a disk method (also called a rotary method), an ultrasonic nozzle method, and the like depending on the spray method, and any of these methods can be applied. From the viewpoint of more easily controlling the total pore volume, the ultrasonic nozzle method is preferable.
  • the first boron nitride aggregated particles and the second boron nitride aggregated particles are manufactured using primary particles of boron nitride as a material.
  • the boron nitride used as the material of the first boron nitride aggregated particles and the second boron nitride aggregated particles is not particularly limited.
  • the boron nitride used as the material is hexagonal boron nitride, cubic boron nitride, boron nitride produced by a reduction nitriding method of a boron compound and ammonia, or nitride produced from a nitrogen compound such as boron compound and melamine.
  • Examples thereof include boron and boron nitride prepared from sodium borohydride and ammonium chloride. From the viewpoint of further effectively increasing the thermal conductivity of the first boron nitride aggregated particles and the second boron nitride aggregated particles, the boron nitride used as the material of the boron nitride aggregated particles is hexagonal boron nitride. It is preferable.
  • the first boron nitride aggregated particles are aggregates of the first boron nitride as primary particles.
  • the second boron nitride aggregated particles are preferably aggregates of second boron nitride as primary particles.
  • the first boron nitride aggregated particles are preferably secondary particles obtained by aggregating the first boron nitride that is primary particles, and the second boron nitride aggregated particles are the second particles that are primary particles. Secondary particles obtained by agglomerating boron nitride are preferable.
  • a granulation step is not necessarily required. It may be boron nitride aggregated particles formed by spontaneously concentrating boron nitride primary particles as the boron nitride crystal grows. Moreover, in order to make the particle diameter of boron nitride aggregated particles uniform, pulverized boron nitride aggregated particles may be used.
  • the first boron nitride aggregated particles are composed of two or more types of aggregated particles having the specific surface area in the above-described range and different particle diameters. Also good.
  • the second boron nitride aggregated particles are composed of two or more types of aggregated particles having the specific surface area and the porosity described above and different particle diameters. It may be configured.
  • the resin material is composed of the first boron nitride aggregated particles and the second boron nitride aggregated particles.
  • third inorganic particles that are not the first boron nitride aggregated particles and the second boron nitride aggregated particles may be included.
  • the resin material preferably contains the third inorganic particles.
  • the third inorganic particles are preferably aggregated particles.
  • the third inorganic particles are preferably secondary particles obtained by agglomerating primary particles of boron nitride.
  • Primary particles constituting the first boron nitride aggregated particle and the second boron nitride aggregated particle (first boron nitride and second boron nitride):
  • the average major axis of the primary particles (first boron nitride) constituting the first boron nitride aggregated particles is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, preferably less than 20 ⁇ m, more preferably 16 ⁇ m or less. .
  • the insulation can be more effectively improved, and the insulation Variation in fracture strength can be more effectively suppressed, and adhesion can be further effectively improved.
  • the average major axis of the primary particles (second boron nitride) constituting the second boron nitride aggregated particles is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, preferably 8 ⁇ m or less, more preferably 7.5 ⁇ m or less. It is.
  • the average major axis of the primary particles (second boron nitride) constituting the second boron nitride aggregated particles is not less than the above lower limit and not more than the above upper limit, the insulating property can be further effectively improved, and the insulation Variation in fracture strength can be more effectively suppressed, and adhesion can be further effectively improved.
  • the average major axis of primary particles (first boron nitride and second boron nitride) constituting the first boron nitride aggregated particles and the second boron nitride aggregated particles can be calculated as follows. .
  • the cross section of the laminate produced by pressing is observed with an electron microscope. From the obtained electron microscope image, the major axis of primary particles (each boron nitride) constituting 50 arbitrarily selected boron nitride aggregate particles is measured, and an average value is calculated.
  • the first boron nitride aggregated particles are configured from the viewpoint of further enhancing the insulating property, from the viewpoint of more effectively suppressing the variation in the dielectric breakdown strength, and from the viewpoint of further effectively improving the adhesiveness.
  • the aspect ratio of the primary particles (first boron nitride) is preferably 3 or more, more preferably 5 or more, preferably 17 or less, more preferably 15 or less.
  • the second boron nitride aggregated particles are configured from the viewpoint of further enhancing the insulating properties, from the viewpoint of more effectively suppressing variation in the dielectric breakdown strength, and from the viewpoint of further effectively improving the adhesiveness.
  • the aspect ratio of the primary particles (second boron nitride) is preferably 2 or more, more preferably 3 or more, preferably 6.5 or less, more preferably 6.1 or less.
  • the aspect ratio of the primary particles (the first boron nitride and the second boron nitride) constituting the first boron nitride aggregated particles and the second boron nitride aggregated particles indicates a major axis / minor axis.
  • the aspect ratio of primary particles (first boron nitride and second boron nitride) constituting the first boron nitride aggregated particles and the second boron nitride aggregated particles can be calculated as follows. .
  • the cross section of the laminate produced by pressing is observed with an electron microscope. From the obtained electron microscope image, the major axis / minor axis of primary particles (each boron nitride) constituting 50 arbitrarily selected boron nitride aggregated particles are measured, and the average value is calculated.
  • the primary particles constituting the first boron nitride aggregated particles and the second boron nitride aggregated particles all the primary particles are in the form of flakes. It is not necessary for the particles to be at least one particle having a bent shape.
  • the bent particles are divided into two particles at the bent portion, and the major axis / minor axis of each particle is measured.
  • the major axis / minor axis of the longer major axis is the major axis / longer axis The minor axis.
  • the aspect ratio is calculated from the obtained major axis / minor axis value.
  • the first boron nitride aggregated particles relatively maintain the morphology of the aggregated particles even after pressing, so confirm from the electron microscopic image of the cross section of the sheet or laminate. it can.
  • the second boron nitride aggregated particles are deformed or collapsed while maintaining isotropic properties after pressing, the existence thereof is strongly suggested.
  • the flakes obtained by crushing the second boron nitride aggregated particles in advance (primary particles constituting the second boron nitride aggregated particles: the second boron nitride), and the first
  • a sheet or a laminate is prepared by mixing boron nitride aggregated particles and a thermosetting resin or the like
  • the above-mentioned scales are relatively easily oriented in the plane direction as compared with the aggregated particles. For this reason, it is difficult for the above-mentioned flakes to remain isotropic even after pressing, compared with the case where aggregated particles are used.
  • the first boron nitride aggregated particles having a large specific surface area and a shape that is relatively easily maintained, and the second boron nitride aggregated particles having a small porosity and a small specific surface area are used because of the large porosity. This can be judged from the electron microscope image of the cross section of the sheet or laminate even after pressing.
  • the resin material according to the present invention includes a binder resin.
  • the binder resin is not particularly limited.
  • a known insulating resin is used as the binder resin.
  • the binder resin preferably includes a thermoplastic component (thermoplastic compound) or a curable component, and more preferably includes a curable component.
  • the curable component include a thermosetting component and a photocurable component.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent. It is preferable that the said photocurable component contains a photocurable compound and a photoinitiator.
  • the binder resin preferably contains a thermosetting component. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.
  • (Meth) acryloyl group means an acryloyl group and a methacryloyl group.
  • (Meth) acryl refers to acrylic and methacrylic.
  • (Meth) acrylate refers to acrylate and methacrylate.
  • thermosetting component thermosetting compound
  • thermosetting compounds include styrene compounds, phenoxy compounds, oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. Can be mentioned.
  • thermosetting compound only 1 type may be used and 2 or more types may be used together.
  • thermosetting compound As the thermosetting compound, (A1) a thermosetting compound having a molecular weight of less than 10,000 (sometimes simply referred to as (A1) thermosetting compound) may be used. A thermosetting compound having a molecular weight (may be simply referred to as (A2) thermosetting compound) may be used, and both (A1) thermosetting compound and (A2) thermosetting compound are used. It may be used.
  • the content of the thermosetting compound in 100% by volume of the resin material is preferably 10% by volume or more, more preferably 20% by volume or more, preferably 90% by volume or less, more preferably 80% by volume or less. .
  • the content of the thermosetting compound is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further enhanced.
  • the content of the thermosetting compound is not more than the above upper limit, the coating property of the resin material is further enhanced.
  • thermosetting compound having a molecular weight of less than 10,000 As a thermosetting compound, the thermosetting compound which has a cyclic ether group is mentioned. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.
  • the thermosetting compound having a cyclic ether group is preferably a thermosetting compound having an epoxy group or an oxetanyl group.
  • thermosetting compound As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.
  • the (A1) thermosetting compound may contain (A1a) a thermosetting compound having an epoxy group (sometimes simply referred to as (A1a) a thermosetting compound), and (A1b) an oxetanyl group.
  • a thermosetting compound (which may be simply referred to as (A1b) thermosetting compound).
  • the (A1) thermosetting compound preferably has an aromatic skeleton.
  • the aromatic skeleton is not particularly limited, and examples thereof include a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, and a bisphenol A skeleton.
  • the aromatic skeleton is preferably a biphenyl skeleton or a fluorene skeleton.
  • thermosetting compound includes an epoxy monomer having a bisphenol skeleton, an epoxy monomer having a dicyclopentadiene skeleton, an epoxy monomer having a naphthalene skeleton, an epoxy monomer having an adamantane skeleton, an epoxy monomer having a fluorene skeleton, and a biphenyl skeleton. Epoxy monomers having a bi (glycidyloxyphenyl) methane skeleton, epoxy monomers having a xanthene skeleton, epoxy monomers having an anthracene skeleton, and epoxy monomers having a pyrene skeleton. These hydrogenated products or modified products may be used.
  • thermosetting compound only 1 type may be used and 2 or more types may be used together.
  • Examples of the epoxy monomer having a bisphenol skeleton include an epoxy monomer having a bisphenol A type, bisphenol F type, or bisphenol S type bisphenol skeleton.
  • Examples of the epoxy monomer having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.
  • Examples of the epoxy monomer having a naphthalene skeleton include 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidyl.
  • Examples include naphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene.
  • Examples of the epoxy monomer having an adamantane skeleton include 1,3-bis (4-glycidyloxyphenyl) adamantane and 2,2-bis (4-glycidyloxyphenyl) adamantane.
  • Examples of the epoxy monomer having a fluorene skeleton include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, and 9,9-bis (4- Glycidyloxy-3-chlorophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-bromophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-Glycidyloxy-3-methoxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dichlorophenyl) Fluorene and 9,9-bis (4-glycidyloxy-3,5-dibromophenyl) Fluorene,
  • Examples of the epoxy monomer having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.
  • Examples of the epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton include 1,1′-bi (2,7-glycidyloxynaphthyl) methane, 1,8′-bi (2,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,7-glycidyloxynaphthyl) methane, 1,8′-bi (3,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,5-glycidyloxynaphthyl) methane 1,8'-bi (3,5-glycidyloxynaphthyl) methane, 1,2'-bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) And methane and 1,2
  • Examples of the epoxy monomer having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl-9H-xanthene.
  • thermosetting compound examples include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3-ethyl- 3-oxetanyl) methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, oxetane-modified phenol novolak, and the like.
  • Only 1 type may be used for a thermosetting compound and 2 or more types may be used together.
  • the (A1) thermosetting compound preferably includes a thermosetting compound having two or more cyclic ether groups.
  • the content of the thermosetting compound having two or more cyclic ether groups is preferably 70% by weight or more in 100% by weight of the (A1) thermosetting compound. More preferably, it is 80% by weight or more, and preferably 100% by weight or less.
  • the content of the thermosetting compound having two or more cyclic ether groups in 100% by weight of the thermosetting compound may be 10% by weight or more and 100% by weight or less. Further, the whole (A1) thermosetting compound may be a thermosetting compound having two or more cyclic ether groups.
  • the molecular weight of the thermosetting compound is less than 10,000.
  • the molecular weight of the thermosetting compound is preferably 200 or more, preferably 1200 or less, more preferably 600 or less, and even more preferably 550 or less.
  • the adhesiveness of the surface of the cured product is lowered, and the handleability of the resin material is further enhanced.
  • the adhesiveness of the cured product is further enhanced. Furthermore, the cured product is hard and hard to be brittle, and the adhesiveness of the cured product is further enhanced.
  • thermosetting compound (A1) when the thermosetting compound is not a polymer, and (A1) when the structural formula of the thermosetting compound can be specified. It means the molecular weight that can be calculated from the structural formula.
  • thermosetting compound (A1) when the thermosetting compound (A1) is a polymer, it means the weight average molecular weight.
  • the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). In gel permeation chromatography (GPC) measurement, tetrahydrofuran is preferably used as the eluent.
  • the content of the (A1) thermosetting compound is preferably 10% by volume or more, more preferably 20% by volume or more, preferably 90% by volume or less, more preferably 80% by volume or less. It is.
  • the content of the thermosetting compound is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further enhanced.
  • the content of the thermosetting compound is not more than the above upper limit, the coating property of the resin material is further enhanced.
  • thermosetting compound having a molecular weight of 10,000 or more (A2) Thermosetting compound having a molecular weight of 10,000 or more: (A2) The thermosetting compound is a thermosetting compound having a molecular weight of 10,000 or more. Since the molecular weight of the (A2) thermosetting compound is 10,000 or more, the (A2) thermosetting compound is generally a polymer, and the above molecular weight generally means a weight average molecular weight.
  • the (A2) thermosetting compound preferably has an aromatic skeleton.
  • the thermosetting compound is a polymer and (A2) the thermosetting compound has an aromatic skeleton, (A2) the thermosetting compound has an aromatic skeleton in any part of the whole polymer. What is necessary is just to have, it may have in the main chain frame
  • the (A2) thermosetting compound preferably has an aromatic skeleton in the main chain skeleton.
  • A2) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.
  • the aromatic skeleton is not particularly limited, and examples thereof include a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, and a bisphenol A skeleton.
  • the aromatic skeleton is preferably a biphenyl skeleton or a fluorene skeleton.
  • thermosetting compound is not particularly limited. Styrene resin, phenoxy resin, oxetane resin, epoxy resin, episulfide compound, (meth) acrylic resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, silicone Examples thereof include resins and polyimide resins.
  • the thermosetting compound is a styrene resin, It is preferably a phenoxy resin or an epoxy resin, more preferably a phenoxy resin or an epoxy resin, and further preferably a phenoxy resin.
  • a phenoxy resin or an epoxy resin further increases the heat resistance of the cured product.
  • use of a phenoxy resin further lowers the elastic modulus of the cured product and further improves the cold-heat cycle characteristics of the cured product.
  • the (A2) thermosetting compound does not need to have cyclic ether groups, such as an epoxy group.
  • styrene resin specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used. Styrene polymers having a styrene-glycidyl methacrylate structure are preferred.
  • styrene monomer examples include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, pn- Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2,4-dimethyl Examples include styrene and 3,4-dichlorostyrene.
  • the phenoxy resin is specifically a resin obtained by reacting, for example, an epihalohydrin and a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound.
  • the phenoxy resin has a bisphenol A skeleton, bisphenol F skeleton, bisphenol A / F mixed skeleton, naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton or dicyclopentadiene skeleton. It is preferable.
  • the phenoxy resin has a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, or a biphenyl skeleton, and at least one of the fluorene skeleton and the biphenyl skeleton. More preferably, it has a skeleton.
  • Use of the phenoxy resin having these preferable skeletons further increases the heat resistance of the cured product.
  • the epoxy resin is an epoxy resin other than the phenoxy resin.
  • the epoxy resins include styrene skeleton-containing epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, and fluorene type epoxy resins. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, epoxy resin having tricyclodecane skeleton, and epoxy resin having triazine nucleus in skeleton Etc.
  • the molecular weight of the thermosetting compound is 10,000 or more.
  • the molecular weight of the thermosetting compound is preferably 30000 or more, more preferably 40000 or more, preferably 1000000 or less, more preferably 250,000 or less.
  • A2 When the molecular weight of the thermosetting compound is not less than the above lower limit, the cured product is hardly thermally deteriorated.
  • the molecular weight of the (A2) thermosetting compound is not more than the above upper limit, the compatibility between the (A2) thermosetting compound and other components is increased. As a result, the heat resistance of the cured product is further increased.
  • the content of the (A2) thermosetting compound is preferably 20% by volume or more, more preferably 30% by volume or more, preferably 60% by volume or less, more preferably 50% by volume or less. It is. (A2) When the content of the thermosetting compound is not less than the above lower limit, the handleability of the resin material is further improved. (A2) When the content of the thermosetting compound is not more than the above upper limit, the coating property of the resin material is further enhanced.
  • thermosetting component thermosetting agent
  • the thermosetting agent is not particularly limited.
  • a thermosetting agent capable of curing the thermosetting compound can be appropriately used.
  • the thermosetting agent includes a curing catalyst.
  • a thermosetting agent only 1 type may be used and 2 or more types may be used together.
  • the thermosetting agent preferably has an aromatic skeleton or an alicyclic skeleton.
  • the thermosetting agent preferably includes an amine curing agent (amine compound), an imidazole curing agent, a phenol curing agent (phenol compound), or an acid anhydride curing agent (acid anhydride), and more preferably includes an amine curing agent. preferable.
  • the acid anhydride curing agent includes an acid anhydride having an aromatic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, It is preferable to include a water additive of an acid anhydride or a modified product of the acid anhydride.
  • the amine curing agent examples include dicyandiamide, imidazole compound, diaminodiphenylmethane, and diaminodiphenylsulfone.
  • the amine curing agent is more preferably dicyandiamide or an imidazole compound.
  • the thermosetting agent preferably includes a curing agent having a melting point of 180 ° C. or higher, and includes an amine curing agent having a melting point of 180 ° C. or higher. Is more preferable.
  • imidazole curing agent examples include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl.
  • phenol curing agent examples include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, xylylene modified novolak, decalin modified novolak, poly ( And di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane.
  • the phenol curing agent is a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group. It is preferable that
  • phenol curing agents include MEH-8005, MEH-8010 and MEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Mitsubishi Chemical), LA-7052, LA-7054, and LA-7751.
  • LA-1356 and LA-3018-50P all of which are manufactured by DIC
  • PS6313 and PS6492 all of which are manufactured by Gunei Chemical Co., Ltd.
  • Examples of the acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, a benzophenone tetracarboxylic acid anhydride, and a pyromellitic acid anhydride.
  • Trimellitic anhydride 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydroanhydride
  • Examples include phthalic acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.
  • Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Also manufactured by Sartomer Japan), ODPA-M and PEPA (all of which are manufactured by Manac), Ricacid MTA-10, Jamaicacid MTA-15, Ricacid TMTA, Jamaicacid TMEG-100, Jamaicacid TMEG-200, Jamaicacid TMEG-300, Ricacid TMEG-500, Jamaicacid TMEG-S, Ricacid TH, Ricacid HT-1A, Jamaicacid HH, Guatemalacid MH-700, Jamaicacid MT-500, Jamaicacid DSDA and Guatemalacid TDA-100 (all manufactured by Shin Nippon Rika) EPICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).
  • the acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. By using these curing agents, the flexibility of the cured product and the moisture resistance and adhesion of the cured product are further increased.
  • Examples of the acid anhydride having an alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid anhydride And the like.
  • Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Jamaicacid HNA and Ricacid HNA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Mitsubishi Chemical Corporation) and the like.
  • thermosetting agent is preferably methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride. Use of methyl nadic anhydride or trialkyltetrahydrophthalic anhydride increases the water resistance of the cured product.
  • the content of the thermosetting agent is preferably 0.1% by volume or more, more preferably 1% by volume or more, preferably 40% by volume or less, more preferably 25% by volume or less. is there.
  • the content of the thermosetting agent is equal to or higher than the lower limit, it becomes much easier to sufficiently cure the thermosetting compound.
  • the content of the thermosetting agent is not more than the above upper limit, it is difficult to generate an excessive thermosetting agent that does not participate in curing. For this reason, the heat resistance and adhesiveness of hardened
  • Photocurable component Photocurable compound
  • the said photocurable compound will not be specifically limited if it has photocurability.
  • As for the said photocurable compound only 1 type may be used and 2 or more types may be used together.
  • the photocurable compound preferably has two or more ethylenically unsaturated bonds.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, and a (meth) acryloyl group.
  • a (meth) acryloyl group is preferred from the viewpoint of effectively advancing the reaction and further suppressing foaming, peeling and discoloration of the cured product.
  • the photocurable compound preferably has a (meth) acryloyl group.
  • the photocurable compound preferably contains epoxy (meth) acrylate.
  • the epoxy (meth) acrylate preferably contains a bifunctional epoxy (meth) acrylate and a trifunctional or higher functional epoxy (meth) acrylate.
  • the bifunctional epoxy (meth) acrylate preferably has two (meth) acryloyl groups.
  • the tri- or higher functional epoxy (meth) acrylate preferably has three or more (meth) acryloyl groups.
  • Epoxy (meth) acrylate is obtained by reacting (meth) acrylic acid with an epoxy compound.
  • Epoxy (meth) acrylate can be obtained by converting an epoxy group into a (meth) acryloyl group. Since the photocurable compound is cured by light irradiation, the epoxy (meth) acrylate preferably has no epoxy group.
  • epoxy (meth) acrylate bisphenol type epoxy (meth) acrylate (for example, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol S type epoxy (meth) acrylate), cresol novolac type Examples include epoxy (meth) acrylate, amine-modified bisphenol-type epoxy (meth) acrylate, caprolactone-modified bisphenol-type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac-type epoxy (meth) acrylate. .
  • the content of the photocurable compound is preferably 5% by volume or more, more preferably 10% by volume or more, preferably 40% by volume or less, more preferably 30% by volume or less.
  • cured material becomes still higher that content of these photocurable compounds is more than the said minimum and below the said upper limit.
  • the photopolymerization initiator is not particularly limited.
  • the photoinitiator which can harden the said photocurable compound by irradiation of light can be used suitably.
  • the photoinitiator only 1 type may be used and 2 or more types may be used together.
  • photopolymerization initiator examples include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, benzoate, acridine, phenazine, Examples include titanocene, ⁇ -aminoalkylphenone, oxime, and derivatives thereof.
  • benzophenone photopolymerization initiator examples include methyl o-benzoylbenzoate and Michler's ketone. EAB (made by Hodogaya Chemical Co., Ltd.) etc. are mentioned as a commercial item of a benzophenone series photoinitiator.
  • acetophenone photopolymerization initiators examples include Darocur 1173, Darocur 2959, Irgacure 184, Irgacure 907, and Irgacure 369 (all of which are manufactured by BASF).
  • benzoin photopolymerization initiators examples include Irgacure 651 (manufactured by BASF).
  • acylphosphine oxide photopolymerization initiators examples include Lucirin TPO and Irgacure 819 (all of which are manufactured by BASF).
  • Examples of commercially available thioxanthone photopolymerization initiators include isopropyl thioxanthone and diethyl thioxanthone.
  • oxime photopolymerization initiators examples include Irgacure OXE-01 and Irgacure OXE-02 (all of which are manufactured by BASF).
  • the content of the photopolymerization initiator with respect to 100 parts by weight of the photocurable compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 20 parts by weight or less, more preferably 15 parts by weight. Less than parts by weight.
  • the photocurable compound can be favorably photocured.
  • the resin material according to the present invention may contain an insulating filler.
  • the insulating filler is not the first boron nitride aggregated particles but the second boron nitride aggregated particles.
  • the insulating filler has an insulating property.
  • the insulating filler may be an organic filler or an inorganic filler. As for the said insulating filler, only 1 type may be used and 2 or more types may be used together.
  • the insulating filler is preferably an inorganic filler. From the viewpoint of more effectively increasing the thermal conductivity, the insulating filler preferably has a thermal conductivity of 10 W / m ⁇ K or more.
  • the thermal conductivity of the insulating filler is preferably 10 W / m ⁇ K or more, more preferably 20 W / m ⁇ K or more.
  • the upper limit of the thermal conductivity of the insulating filler is not particularly limited. Inorganic fillers having a thermal conductivity of about 300 W / m ⁇ K are widely known, and inorganic fillers having a thermal conductivity of about 200 W / m ⁇ K are easily available.
  • the material of the insulating filler is not particularly limited.
  • Materials for the insulating filler include nitrogen compounds (boron nitride, aluminum nitride, silicon nitride, carbon nitride, titanium nitride, etc.), carbon compounds (silicon carbide, fluorine carbide, boron carbide, titanium carbide, tungsten carbide, diamond, etc.) ), And metal oxides (such as silica, alumina, zinc oxide, magnesium oxide, and beryllium oxide).
  • the material of the insulating filler is preferably the nitrogen compound, the carbon compound or the metal oxide, and more preferably alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide. preferable. Use of these preferable insulating fillers further increases the thermal conductivity of the cured product.
  • the insulating filler is preferably spherical particles, or non-aggregated particles and agglomerated particles having an aspect ratio of more than 2. Use of these insulating fillers further increases the thermal conductivity of the cured product.
  • the spherical particles have an aspect ratio of 2 or less.
  • the new Mohs hardness of the insulating filler material is preferably 12 or less, more preferably 9 or less. When the new Mohs hardness of the insulating filler material is 9 or less, the workability of the cured product is further enhanced.
  • the material of the insulating filler is preferably boron nitride, synthetic magnesite, crystalline silica, zinc oxide, or magnesium oxide.
  • the new Mohs hardness of these inorganic filler materials is 9 or less.
  • the particle size of the insulating filler is preferably 0.1 ⁇ m or more, and preferably 20 ⁇ m or less.
  • the particle diameter is not less than the above lower limit, the insulating filler can be easily filled at a high density.
  • the particle diameter is not more than the above upper limit, the thermal conductivity of the cured product is further increased.
  • the above particle diameter means an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring apparatus.
  • the particle diameter of the insulating filler is preferably calculated by sampling 3 g of the insulating filler and averaging the particle diameter of the insulating filler contained therein.
  • the average particle diameter of an insulating filler it is preferable to employ
  • the content of the insulating filler in 100% by volume of the resin material is preferably 1% by volume or more, more preferably 3% by volume or more, preferably 20%. Volume% or less, More preferably, it is 10 volume% or less.
  • the resin material may contain, in addition to the components described above, other components generally used for resin materials such as dispersants, chelating agents, antioxidants, resin sheets, and curable sheets.
  • the resin material may be a paste or a curable paste.
  • the resin material may be a resin sheet or a curable sheet.
  • a cured product can be obtained by curing the resin material.
  • cured material is a hardened
  • the resin material may be prepared by laminating two or more resin sheets.
  • the resin sheet which concerns on this invention may be sufficient as one layer or more among the resin sheets of two or more layers.
  • the laminate according to the present invention includes a heat conductor, an insulating layer, and a conductive layer.
  • the insulating layer is laminated on one surface of the heat conductor.
  • the conductive layer is laminated on the surface of the insulating layer opposite to the heat conductor side.
  • the insulating layer may be laminated on the other surface of the heat conductor.
  • the material of the insulating layer is the resin material described above.
  • Thermal conductor The thermal conductivity of the thermal conductor is preferably 10 W / m ⁇ K or more.
  • An appropriate heat conductor can be used as the heat conductor.
  • the heat conductor is preferably a metal material. Examples of the metal material include a metal foil and a metal plate.
  • the heat conductor is preferably the metal foil or the metal plate, and more preferably the metal plate.
  • the metal material examples include aluminum, copper, gold, silver, and a graphite sheet. From the viewpoint of more effectively increasing the thermal conductivity, the metal material is preferably aluminum, copper, or gold, and more preferably aluminum or copper.
  • the metal for forming the conductive layer is not particularly limited.
  • the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof.
  • the metal include tin-doped indium oxide (ITO) and solder. From the viewpoint of more effectively increasing the thermal conductivity, aluminum, copper or gold is preferable, and aluminum or copper is more preferable.
  • the method for forming the conductive layer is not particularly limited.
  • Examples of the method for forming the conductive layer include a method by electroless plating, a method by electroplating, and a method in which the insulating layer and the metal foil are thermocompression bonded. Since the formation of the conductive layer is simple, a method of thermocompression bonding the insulating layer and the metal foil is preferable.
  • FIG. 1 is a cross-sectional view schematically showing a resin sheet according to an embodiment of the present invention.
  • the actual size and thickness are different for convenience of illustration.
  • a resin sheet 1 (resin material) shown in FIG. 1 includes a binder resin 11, first boron nitride aggregated particles 12, and second boron nitride aggregated particles 13.
  • the first boron nitride aggregated particles 12 and the second boron nitride aggregated particles 13 are preferably the first boron nitride aggregated particles and the second boron nitride aggregated particles described above.
  • the specific surface area of the first boron nitride aggregated particles 12 and the specific surface area of the second boron nitride aggregated particles 13 are different.
  • the porosity of the second boron nitride aggregated particles 13 is 35% or more.
  • the binder resin 11 includes a curable component.
  • the binder resin 11 may include a thermosetting component including a thermosetting compound and a thermosetting agent, or may include a photocurable component including a photocurable compound and a photopolymerization initiator.
  • the binder resin is preferably not completely cured.
  • the binder resin may be B-staged by heating or the like.
  • the binder resin may be a B-staged product that has been B-staged.
  • the resin sheet there may be voids inside the sheet.
  • a gap may exist between the first boron nitride aggregated particles and the second boron nitride aggregated particles.
  • FIG. 2 is a cross-sectional view schematically showing a laminate obtained using the resin material according to one embodiment of the present invention.
  • the actual size and thickness are different for convenience of illustration.
  • the 2 includes a heat conductor 22, an insulating layer 23, and a conductive layer 24.
  • the heat conductor 22, the insulating layer 23, and the conductive layer 24 are the above-described heat conductor, insulating layer, and conductive layer.
  • the resin sheet 1 shown in FIG. 1 is used as the insulating layer 23.
  • the heat conductor 22 has one surface 22a (first surface) and the other surface 22b (second surface).
  • the insulating layer 23 has one surface 23a (first surface) and the other surface 23b (second surface).
  • the conductive layer 24 has one surface 24a (first surface) and the other surface 24b (second surface).
  • a conductive layer 24 is laminated on one surface 23 a (first surface) side of the insulating layer 23.
  • the heat conductor 22 is laminated on the other surface 23b (second surface) side of the insulating layer 23.
  • An insulating layer 23 is stacked on the other surface 24 b (second surface) side of the conductive layer 24.
  • An insulating layer 23 is laminated on one surface 22 a (first surface) side of the heat conductor 22.
  • An insulating layer 23 is disposed between the heat conductor 22 and the conductive layer 24.
  • the method for producing the laminate is not particularly limited. As a manufacturing method of the said laminated body, the method etc. which laminate
  • the insulating layer 23 includes the cured product portion 14, the first boron nitride aggregated particles 12, and the second boron nitride aggregated particles 13.
  • the insulating layer 23 is formed by the resin sheet 1 shown in FIG.
  • the insulating layer is preferably formed by heat-pressing the resin sheet with a vacuum press or the like.
  • the first boron nitride aggregated particles 12 are preferably not deformed or collapsed by a compression force such as a press, and the shape is preferably maintained.
  • the first boron nitride aggregated particles 12 are preferably present in the form of aggregated particles (secondary particles) in the cured product.
  • the second boron nitride aggregated particles 13 may be deformed or collapsed by a compression force such as a press.
  • the second boron nitride agglomerated particles 13 may be deformed agglomerated particles (secondary particles), or may be primary particles by the collapse of the agglomerated particles (secondary particles).
  • the second boron nitride aggregated particles 13 may exist in the form of deformed aggregated particles (secondary particles) in the cured product, and the aggregated particles (secondary particles) collapse to form primary particles. May exist.
  • the second boron nitride aggregated particles 13 are deformed or collapsed around the first boron nitride aggregated particles 12.
  • the deformed or collapsed second boron nitride aggregated particles 13 are present between the first boron nitride aggregated particles 12.
  • the deformed or collapsed second boron nitride aggregated particles 13 can fill the voids existing between the first boron nitride aggregated particles 12, and can effectively enhance the insulation.
  • the laminated body 21 can fill the gaps between the first boron nitride aggregated particles 12 without gaps by the second boron nitride aggregated particles 13, it is possible to effectively suppress variations in dielectric breakdown strength. it can.
  • the cured product portion 14 is a portion where the binder resin 11 is cured.
  • the cured product portion 14 is obtained by curing the binder resin 11.
  • the cured product portion 14 may be a portion where a thermosetting component including a thermosetting compound and a thermosetting agent is cured, or a portion where a photocurable component including a photocurable compound and a photopolymerization initiator is cured. There may be.
  • cured material part 14 is obtained by hardening a thermosetting component or a photocurable component.
  • the resin material and the cured product can be used in various applications that require high thermal conductivity, mechanical strength, and the like.
  • the laminate is used by being disposed between a heat generating component and a heat radiating component.
  • the laminated body is used as a heat radiating body installed between a CPU and a fin, or a heat radiating body for a power card used in an inverter of an electric vehicle.
  • the laminated body can be used as an insulating circuit substrate by forming a circuit of the conductive layer of the laminated body by a technique such as etching.
  • Thermosetting compound (1) “Epicoat 828US” manufactured by Mitsubishi Chemical Corporation, epoxy compound (2) “DL-92” manufactured by Meiwa Kasei Co., Ltd., phenol novolac compound
  • Thermosetting agent (1) “Dicyandiamide” manufactured by Tokyo Chemical Industry Co., Ltd. (2) “2MZA-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd., isocyanuric modified solid dispersion type imidazole
  • First boron nitride aggregated particles (including alternatives): (1) “PTX60S” manufactured by Momentive (2) “PCTH7MHF” manufactured by Saint-Gobain (3) Momentive “PT350” (4) “AC6091” manufactured by Momentive (5) Boron nitride aggregated particles 3
  • Second boron nitride aggregated particles (including alternatives): (1) Boron nitride aggregated particles 1 (2) Boron nitride agglomerated particles 2 (3) Boron nitride aggregated particles 4 (4) “AC6091” manufactured by Momentive (5) “PTX25” manufactured by Momentive
  • boron nitride aggregated particle 1 Boron nitride primary particles having an average major axis of 7.2 ⁇ m and an aspect ratio of 5.3 were produced by agglomeration by a spray drying method so that the porosity was 44% and the average particle size was 40 ⁇ m. The porosity was measured with a mercury porosimeter, and the porosity when only the voids of 5 ⁇ m or less were used as the intraparticle voids was calculated. The porosity was measured by the same method as the method for measuring the porosity of the first boron nitride aggregated particles and the second boron nitride aggregated particles described later.
  • boron nitride agglomerated particles 2 Boron nitride primary particles having an average major axis of 6.5 ⁇ m and an aspect ratio of 6.1 were produced by agglomeration by a spray drying method so that the porosity was 39% and the average particle size was 30 ⁇ m.
  • boron nitride aggregated particles 3 Boron nitride primary particles having an average major axis of 7 ⁇ m and an aspect ratio of 12 were produced by agglomeration by a spray drying method so that the porosity was 65% and the average particle size was 35 ⁇ m.
  • boron nitride aggregated particles 4 Boron nitride primary particles having an average major axis of 9 ⁇ m and an aspect ratio of 6 were produced by agglomeration by a spray drying method so that the porosity was 48% and the average particle size was 80 ⁇ m.
  • a method for measuring the specific surface area of the first boron nitride aggregated particles and the second boron nitride aggregated particles in pores having a pore diameter of more than 0 ⁇ m and 5 ⁇ m or less Using a mercury porosimeter “pore master 60” manufactured by QUANTACHROME, the cumulative amount of mercury intrusion was measured against the pressure applied by the mercury intrusion method. 0.2 to 0.3 g of boron nitride aggregated particles were weighed and measured in a low pressure mode and a high pressure mode. From the obtained data, a distribution curve indicating the pore volume per unit section of the pore diameter was obtained.
  • the specific surface areas of the first boron nitride aggregated particles and the second boron nitride aggregated particles were calculated. Specifically, using the pore diameter (d ( ⁇ m)) obtained by the measurement and the pore volume difference ( ⁇ V (cc / g)), the specific surface area ( ⁇ S) in each pore by the following formula: (M 2 / g)) was calculated.
  • the pore volume difference in the boron nitride agglomerated particles used in the present invention, the pore volume approaches 0 once in the vicinity of 5 ⁇ m. This is considered to indicate the pores inside the particles. Therefore, the specific surface area was calculated by adding ⁇ S in pores having a pore diameter exceeding 0 ⁇ m and not more than 5 ⁇ m.
  • Method for measuring porosity of first boron nitride aggregated particles and second boron nitride aggregated particles By the method described above, a distribution curve indicating the pore volume per unit section of the pore diameter was obtained. Based on the distribution curve, a value (V) obtained by subtracting the voids between the aggregated particles from the total voids was calculated. From the obtained distribution curve, voids having a pore diameter of 5 ⁇ m or more were defined as voids between aggregated particles.
  • the porosity ( ⁇ ) can be expressed by the following formula.
  • the porosity (%) was calculated by substituting the value of V calculated for each boron nitride aggregated particle into the above formula.
  • the particle diameters of the first boron nitride aggregated particles and the second boron nitride aggregated particles were measured using a “laser diffraction particle size distribution measuring apparatus” manufactured by Horiba, Ltd. By sampling the particle diameters of the first boron nitride aggregate particles and the second boron nitride aggregate particles for each 3 g of the boron nitride aggregate particles, and averaging the particle diameters of the boron nitride aggregate particles contained therein Calculated.
  • the particle diameter (d50) of the boron nitride aggregated particles when the cumulative volume is 50% is the average particle size. The diameter.
  • the average major axis of primary particles (first boron nitride and second boron nitride) constituting the first boron nitride aggregated particles and the second boron nitride aggregated particles was measured as follows.
  • Method for measuring average major axis of primary particles (first boron nitride and second boron nitride) constituting first boron nitride aggregated particles and second boron nitride aggregated particles Cross section of a laminate prepared by mixing primary particles (first boron nitride and second boron nitride) constituting the first boron nitride aggregated particles and second boron nitride aggregated particles with a thermosetting resin or the like From the electron microscope image, the major diameter of primary particles (each boron nitride) constituting 50 arbitrarily selected boron nitride aggregated particles was measured, and the average value was calculated.
  • ⁇ The difference between the maximum value and the minimum value of the dielectric breakdown strength is less than 20 kV / mm.
  • ⁇ The difference between the maximum value and the minimum value of the dielectric breakdown strength is 20 kV / mm or more and less than 40 kV / mm.
  • the difference between the maximum value and the minimum value is 40 kV / mm or more
  • Adhesiveness (peel strength) The obtained curable sheet (insulating layer 350 ⁇ m) was heated at 200 ° C. for 1 hour while being pressed between an electrolytic copper foil (thickness 35 ⁇ m) and an aluminum plate (thickness 1 mm) at a pressure of 10 MPa to prepare a measurement sample. Obtained. Then, the measurement sample was cut out into 5 cm x 12 cm, only the center 1 cm x 12 cm of the short side was left, and the copper foil of the remaining part was peeled off. The peel strength between the center 1 cm electrolytic copper foil and the cured insulating layer was measured by a 90 ° peel test. Adhesiveness (peel strength) was determined according to the following criteria.
  • Peel strength is 5 N / cm or more
  • peel strength is 2 N / cm or more and less than 5 N / cm
  • Peel strength is less than 2 N / cm

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Abstract

L'invention concerne une matière à base de résine qui peut efficacement améliorer les propriétés d'isolation, qui peut supprimer efficacement une variation de la résistance au claquage diélectrique et qui peut en outre augmenter efficacement l'adhérence. Ce matériau de résine contient des premières particules d'agrégat de nitrure de bore, des deuxièmes particules d'agrégat de nitrure de bore et une résine liante. La surface spécifique est supérieure ou égale à 1,3 m²/g dans les pores dans les premières particules d'agrégat de nitrure de bore qui présentent un diamètre de pore supérieur à 0 µm et inférieur ou égal à 5 µm, la surface spécifique est inférieure à 1,3 m²/g dans les pores dans les deuxièmes particules d'agrégat de nitrure de bore qui présentent un diamètre de pore supérieur à 0 µm et inférieur ou égal à 5 µm et la porosité des deuxièmes particules d'agrégat de nitrure de bore est supérieure ou égale à 35 %.
PCT/JP2018/002719 2017-01-30 2018-01-29 Matière et stratifié à base de résine WO2018139642A1 (fr)

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WO2020138335A1 (fr) * 2018-12-27 2020-07-02 住友化学株式会社 Poudre inorganique pour composition de résine de dissipation de chaleur, composition de résine de dissipation de chaleur l'utilisant, et procédés de production de celle-ci
WO2023275800A1 (fr) * 2021-06-30 2023-01-05 3M Innovative Properties Company Précurseur de feuille thermoconductrice, composition de précurseur, feuille thermoconductrice obtenue à partir du précurseur de feuille thermoconductrice, et son procédé de production
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WO2023275800A1 (fr) * 2021-06-30 2023-01-05 3M Innovative Properties Company Précurseur de feuille thermoconductrice, composition de précurseur, feuille thermoconductrice obtenue à partir du précurseur de feuille thermoconductrice, et son procédé de production
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JP7357181B1 (ja) * 2021-12-27 2023-10-05 デンカ株式会社 窒化ホウ素粒子及び放熱シート

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