WO2022209335A1 - Feuille composite et son procédé de fabrication, et stratifié et son procédé de fabrication - Google Patents

Feuille composite et son procédé de fabrication, et stratifié et son procédé de fabrication Download PDF

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Publication number
WO2022209335A1
WO2022209335A1 PCT/JP2022/005177 JP2022005177W WO2022209335A1 WO 2022209335 A1 WO2022209335 A1 WO 2022209335A1 JP 2022005177 W JP2022005177 W JP 2022005177W WO 2022209335 A1 WO2022209335 A1 WO 2022209335A1
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Prior art keywords
resin
sheet
curing
composite sheet
resin composition
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PCT/JP2022/005177
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English (en)
Japanese (ja)
Inventor
仁孝 南方
政秀 金子
亮 吉松
真也 坂口
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Denka Co Ltd
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Denka Co Ltd
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Priority to JP2022528624A priority Critical patent/JP7148758B1/ja
Publication of WO2022209335A1 publication Critical patent/WO2022209335A1/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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/83—Macromolecular compounds

Definitions

  • the present disclosure relates to a composite sheet and its manufacturing method, and a laminate and its manufacturing method.
  • Components such as power devices, transistors, thyristors, and CPUs are required to efficiently dissipate the heat generated during use.
  • a composite composed of a resin and a ceramic such as boron nitride is used as a heat dissipation member.
  • a composite obtained by impregnating a porous ceramic sintered body for example, a boron nitride sintered body
  • a resin-impregnated boron nitride sintered body the primary particles constituting the boron nitride sintered body are brought into direct contact with the circuit board to reduce the thermal resistance of the laminate and improve heat dissipation. is also being studied (see Patent Document 2, for example).
  • the resin part is maintained in a semi-cured state, and the adhesion is improved by further curing the resin when connecting to an adherend such as a metal sheet.
  • the inventors of the present invention have found that the resin is in a semi-cured state and becomes fluid due to heating at the time of connection, so that part of the resin flows out from the side of the composite, reducing the amount of resin in the composite, voids, etc. It has been found that the insulation may not be exhibited to the extent expected. The present disclosure is made based on this finding.
  • One aspect of the present disclosure is a composite sheet including a porous nitride sintered plate and a resin filled in the pores of the nitride sintered plate, the composite sheet having a hardened region including the outer periphery of the sheet. and a composite sheet in which the curing rate of the resin in the cured region is higher than the curing rate of the resin in the other regions.
  • the above-mentioned composite sheet has a cured region having a higher curing rate than other regions in the region including the outer periphery, thereby suppressing the resin from flowing out when connecting to the adherend, and the obtained adherend is excellent. Insulating properties can be exhibited.
  • the curing rate of the resin in the region other than the cured region is lower than that in the cured region, the adhesiveness to the adherend can also be ensured.
  • the hardened region may be provided over the entire outer periphery of the sheet. By providing the hardening region over the entire circumference of the outer periphery of the sheet, it is possible to further suppress the outflow of the resin when connecting to the adherend, and further improve the insulation properties of the obtained laminate. can.
  • the hardened region may extend along the thickness direction of the sheet.
  • the width of the cured region in a cross section along the thickness direction of the sheet may be 1 to 20% of the total length of the sheet.
  • both adhesion to the adherend and insulating properties of the laminate obtained by connection to the adherend can be achieved at a higher level.
  • the cured region may be a resin layer provided on the side surface of the nitride sintered plate.
  • the above resin may contain a thermosetting resin.
  • a thermosetting resin By including a thermosetting resin in the resin, curing can be accelerated when connecting to an adherend, and the outflow of the resin from areas other than the cured resin of the composite sheet can be further suppressed.
  • the difference between the maximum value and the minimum value of the curing rate of the resin may be 30% or more.
  • the difference between the curing rate of the resin in the cured region (corresponding to the maximum value) and the curing rate of the resin in the other regions (corresponding to the minimum value) is 30% or more, the resin outflow can be further reduced, and sufficient adhesiveness can be ensured.
  • the curing rate of the resin in the curing region may be 60% or more.
  • One aspect of the present disclosure provides a laminate comprising the composite sheet described above and a metal sheet provided on the composite sheet.
  • the laminate includes the above-described composite sheet, it can exhibit excellent insulating properties.
  • One aspect of the present disclosure includes an impregnation step of impregnating a porous nitride sintered plate with a resin composition to obtain a resin-impregnated sheet, and heating the resin-impregnated sheet to heat the resin composition filled in the mechanism.
  • a first curing step of semi-curing, and a second curing step of curing or semi-curing the resin composition by irradiating a region including the outer periphery of the resin-impregnated sheet with heat or laser light. provides a method of manufacturing a composite sheet.
  • a hardened region can be formed in the region including the outer peripheral edge of the sheet by performing a plurality of treatments for promoting the hardening reaction on the region including the outer peripheral edge.
  • the composite sheet described above can be manufactured.
  • One aspect of the present disclosure is a first impregnation step of obtaining a first resin-impregnated sheet by impregnating a region including the outer periphery of a porous nitride sintered plate with a first resin composition, and the first resin-impregnated sheet.
  • a first curing step of curing or semi-curing the first resin composition filled in the pores by heating to obtain a first resin-filled sheet containing a resin in a region including the outer peripheral edge; and the first resin-filled sheet
  • a second impregnation step of obtaining a second resin-impregnated sheet by impregnating the second resin composition into the and a method for manufacturing a composite sheet.
  • the region including the outer periphery of the nitride sintered plate is preliminarily impregnated with the first resin composition, cured or semi-cured, and then the entire surface of the nitride sintered plate is impregnated with the second resin composition. and hardening or semi-hardening.
  • the area including the outer edge of the sheet is subjected to a plurality of treatments for accelerating the curing reaction, and the curing of this area progresses more than the other areas. Therefore, the composite sheet described above can be manufactured.
  • One aspect of the present disclosure includes an impregnation step of impregnating a porous nitride sintered plate with a resin composition to obtain a resin-impregnated sheet, and heating the resin-impregnated sheet to obtain the resin composition filled in the pores.
  • the side surface of the resin-filled sheet is coated with a third resin having a higher curing rate than the resin constituting the resin-filled sheet.
  • One aspect of the present disclosure provides a method for manufacturing a laminate, which includes a lamination step of laminating the composite sheet obtained by the above-described manufacturing method and a metal sheet, and heating and pressurizing them.
  • the above manufacturing method uses the above composite sheet, it is possible to provide a laminate capable of exhibiting excellent insulation.
  • the present disclosure it is possible to provide a composite sheet that has excellent adhesion to an adherend and can exhibit excellent insulating properties after being adhered to an adherend. According to the present disclosure, it is also possible to provide a laminate having excellent insulating properties and a method for manufacturing the same.
  • FIG. 1 is a perspective view showing an example of a composite sheet.
  • FIG. 2 is a schematic diagram showing a cross section along line II-II in FIG.
  • FIG. 3 is a schematic cross-sectional view showing another example of the composite sheet.
  • FIG. 4 is a cross-sectional view showing an example of a laminate.
  • each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. .
  • One embodiment of the composite sheet includes a porous nitride sintered plate and resin filled in the pores of the nitride sintered plate.
  • the composite sheet has a hardening region including the outer periphery of the sheet, and the hardening rate of the resin in the hardening region is higher than the hardening rate of the resin in the other regions.
  • the shape of the sheet is not particularly limited, it is generally rectangular parallelepiped.
  • FIG. 1 is a perspective view showing an example of a composite sheet.
  • FIG. 2 is a schematic diagram showing a cross section along line II-II of FIG.
  • the composite sheet 10 has a hardened region 14 provided around the outer periphery of the sheet and a region surrounded by the hardened region 14 (another region 12).
  • the composite sheet 10 is shown as an example in which the cured region 14 is provided continuously over the entire outer periphery of the sheet, but it may be provided discontinuously. From the viewpoint of suppressing outflow of the resin when the composite sheet 10 is heat-treated, it is more desirable that the cured region 14 is continuously provided over the entire circumference of the outer peripheral edge.
  • Whether or not it is the cured area 14 can be confirmed by checking whether the resin hardening rate is large at the outer peripheral edge of the sheet with reference to the hardening rate of the resin in the central region of the main surface of the composite sheet 10 . Simply, it can be done by examining the calorific value by differential scanning calorimetry of a resin sample collected from the relevant location (for example, an area of about 1 mm from the outer peripheral edge toward the center including the outer peripheral edge).
  • the cured region 14 extends along the thickness direction of the sheet and is shown as an example formed continuously with a uniform width.
  • the widths t ⁇ b>1 and t ⁇ b>2 of the cured regions 14 in the cross section along the sheet thickness direction can be adjusted according to the performance required of the composite sheet 10 .
  • the width of the cured region 14 may be, for example, 20% or less, 15% or less, or 10% or less based on the total length L of the composite sheet 10 .
  • the width of the hardened region 14 may be, for example, 1% or more, 3% or more, or 5% or more based on the total length L of the composite sheet 10 in the same cross section.
  • the width of the cured region 14 may be adjusted within the above range, and may be, for example, 1-20% or 5-10% of the total length L of the composite sheet 10 .
  • the widths t1 and t2 of the hardened region may be the same or different, but even if they are different, it is desirable that both the widths t1 and t2 of the hardened region are within the above range.
  • the thickness of the composite sheet 10 may be, for example, less than 10.0 mm, 5.0 mm or less, or 2.0 mm or less.
  • the lower limit of the thickness of the composite sheet 10 may be, for example, 0.1 mm or more, 0.2 mm or more, or 0.3 mm or more. This allows the composite sheet 10 to be sufficiently miniaturized.
  • Such a composite sheet 10 is suitably used as a part of a semiconductor device, for example.
  • the thickness of the composite sheet 10 may be adjusted within the ranges described above, and may be, for example, 0.1-10.0 mm, or 0.2-2.0 mm.
  • the thickness of the composite sheet 10 is measured along the direction perpendicular to the main surface.
  • the thickness of the composite sheet 10 is not constant, the thickness is measured at 10 arbitrary points, and the arithmetic mean value thereof should be within the above range.
  • the size of the composite sheet 10 is not particularly limited, and may be, for example, 50 mm 2 or more, 200 mm 2 or more, 500 mm 2 or more, 800 mm 2 or more, or 1000 mm 2 or more.
  • porous nitride sintered plates include boron nitride sintered plates.
  • the nitride sintered plate contains nitride particles and pores formed by sintering nitride primary particles.
  • the median pore size of the pores of the nitride sintered plate may be, for example, 6.0 ⁇ m or less, 5.0 ⁇ m or less, 4.0 ⁇ m or less, or 3.5 ⁇ m or less. Since such a nitride sintered plate has a small pore size, it is possible to sufficiently increase the contact area between the nitride particles. Therefore, thermal conductivity can be increased.
  • the median pore diameter of the pores of the nitride sintered plate may be, for example, 0.3 ⁇ m or more, 0.5 ⁇ m or more, 1.0 ⁇ m or more, or 1.5 ⁇ m or more. Since such a nitride sintered plate can be sufficiently deformed by pressurization during bonding, it has excellent adhesion to other members (adherends).
  • the median pore size of the pores of the nitride sintered plate may be adjusted within the above range, and may be, for example, 0.3-6.0 ⁇ m.
  • the median pore diameter of the pores of the nitride sintered plate can be measured by the following procedure. First, the composite is heated to remove the semi-cured resin layer and the first resin. Then, using a mercury porosimeter, the pore size distribution is determined when the nitride sintered plate is pressed while increasing the pressure from 0.0042 MPa to 206.8 MPa. When the horizontal axis is the pore diameter and the vertical axis is the cumulative pore volume, the pore diameter when the cumulative pore volume reaches 50% of the total pore volume is the median pore diameter. As the mercury porosimeter, for example, one manufactured by Shimadzu Corporation can be used.
  • the porosity of the nitride sintered plate that is, the ratio of the pore volume (V1) in the nitride sintered plate may be 30 to 65% by volume, and may be 40 to 60% by volume. If the porosity becomes too large, the strength of the nitride sintered plate tends to decrease. On the other hand, if the porosity is too small, less resin tends to ooze out when the composite is adhered to another member.
  • the porosity is obtained by calculating the bulk density [B (kg/m 3 )] from the volume and mass of the nitride sintered plate, and using this bulk density and the theoretical density [A (kg/m 3 )] of the nitride. , can be obtained by the following formula (1).
  • the nitride sintered plate may contain at least one selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride.
  • the theoretical density A is 2280 kg/m 3 .
  • aluminum nitride the theoretical density A is 3260 kg/m 3 .
  • silicon nitride the theoretical density A is 3170 kg/m 3 .
  • Porosity (volume%) [1-(B/A)] x 100 (1)
  • the bulk density B may be 800 to 1500 kg/m 3 or 1000 to 1400 kg/m 3 . If the bulk density B becomes too small, the strength of the nitride sintered plate tends to decrease. On the other hand, if the bulk density B is too high, the amount of resin filled in the composite may decrease, resulting in a loss of good adhesion of the composite.
  • the thickness of the nitride sintered plate may be, for example, 10.0 mm or less, 5.0 mm or less, or 2.0 mm or less.
  • the lower limit of the thickness of the nitride sintered plate may be, for example, 0.1 mm or more, 0.2 mm or more, 0.3 mm or more, or 0.5 mm or more.
  • the thickness of the nitride sintered plate may be adjusted within the above range, and may be, for example, 0.1-10.0 mm, or 0.3-2.0 mm.
  • the thickness of the nitride sintered plate is measured along the direction orthogonal to the main surface, and if the thickness is not constant, select 10 arbitrary locations to measure the thickness, and the arithmetic average value is It is sufficient if it is in the range described above.
  • the resin contained in the composite sheet 10 is a cured product (C stage) or semi-cured product (B stage) of a resin composition containing a main agent and a curing agent.
  • the cured product is obtained by completing the curing reaction of the resin composition.
  • the semi-cured product is obtained by partially progressing the curing reaction of the resin composition.
  • the semi-cured product can be further cured by a subsequent curing treatment.
  • the resin may contain a thermosetting resin or the like that is generated by the reaction of the main agent and curing agent in the resin composition.
  • the semi-cured product may contain monomers such as a main agent and a curing agent in addition to the thermosetting resin as a resin component. It can be confirmed by a differential scanning calorimeter, for example, that the resin contained in the composite sheet 10 is a semi-cured product (B stage) before becoming a cured product (C stage).
  • the curing rate of the resin in the cured region 14 of the composite sheet 10 is in a state of being more advanced than the curing rate of the resin in the other regions.
  • the curing rate of the resin in the cured region 14 may be, for example, 40% or more, 50% or more, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more.
  • the curing rate of the resin in the cured region 14 is within the above range, it is possible to further suppress the resin from flowing out of the composite sheet 10 from other regions during adhesion to the adherend, and the insulating property of the obtained laminate is improved. can be further improved.
  • the upper limit of the curing rate of the resin in the curing region 14 is not particularly limited, but may be, for example, 90% or less, 88% or less, or 86% or less.
  • the cure rate of the resin in the cure zone 14 may be adjusted within the ranges described above, and may be, for example, 20-90%, 50-86%, or 60-86%.
  • the difference between the maximum value and the minimum value of the curing rate of the resin in the composite sheet 10 is desirably 10% or more, 20% or more, or 30% or more.
  • the difference may be, for example, the difference between the curing rate of the resin in the cured region (corresponding to the maximum value) and the curing rate of the resin in the other region (corresponding to the minimum value).
  • the difference may be, for example, 35% or more, 40% or more, 45% or more, or 50% or more.
  • the difference may be 80% or less, 70% or less, or 60% or less.
  • the difference between the maximum value and the minimum value of the curing rate of the resin in the composite sheet 10 may be adjusted within the range described above, and may be, for example, 10-80% or 30-60%.
  • the cure rate of the resin herein can be determined by measurement using a differential scanning calorimeter. First, the calorific value Q per unit mass generated when 2 mg of the uncured resin composition is completely cured is measured. Then, a 10 mg sample taken from the resin included in the composite sheet is heated in the same manner, and the calorific value R per unit mass generated when the sample is completely cured is determined. At this time, the mass of the sample used for the measurement with the differential scanning calorimeter is the same as that of the resin composition used for the measurement of the calorific value Q. Assuming that c (% by mass) of a thermosetting component is contained in the resin, the curing rate of the resin composition impregnated in the composite sheet is obtained by the following formula (A).
  • Resins include, for example, epoxy resins, silicone resins, cyanate resins, silicone rubbers, acrylic resins, phenolic resins, melamine resins, urea resins, bismaleimide resins, unsaturated polyesters, fluororesins, polyimides, polyamideimides, polyetherimides, poly Butylene terephthalate, polyethylene terephthalate, polyphenylene ether, polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide resin, maleimide-modified resin, ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber/styrene) resin, AES (acrylonitrile/ethylene/propylene/diene rubber-styrene) resin, polyglycolic acid resin, polyphthalamide, and polyacetal.
  • epoxy resins silicone resins, cyanate resins,
  • a modification of the composite sheet may be, for example, a sintered nitride plate with a resin layer on the outer peripheral side surface.
  • the cured region of the composite sheet may be composed of the resin layer, and the other region may be a nitride sintered plate (resin-impregnated body) impregnated with resin.
  • FIG. 3 is a schematic cross-sectional view showing another example of the composite sheet.
  • the composite sheet 10 has a resin-impregnated body 13 and a resin layer 15 provided on the outer peripheral side surface of the resin-impregnated body 13 .
  • the resin layer 15 corresponds to the cured region
  • the resin-impregnated body 13 corresponds to other regions.
  • the component of the resin layer 15 may be the same as or different from the resin constituting the resin-impregnated body 13, but it improves the adhesiveness between the resin-impregnated body 13 and the resin layer 15, From the viewpoint of improving the insulation after adhering to the body, it is desirable to be composed of the same resin.
  • the composite sheet 10 described above is useful for forming a laminate that requires a high degree of insulation, such as a laminate that is laminated with a metal sheet or the like, because the outflow of the resin during heating is suppressed.
  • a laminate includes the composite sheet and a metal sheet provided on the composite sheet.
  • the composite sheet and the metal sheet may be joined by a cured resin of the composite sheet.
  • the composite sheet and the metal sheet are joined via a cured resin.
  • the metal sheet is not particularly limited as long as it is made of metal and has a sheet shape.
  • the adherend (another member) mentioned in the description of the composite above may be a metal sheet.
  • the metal sheet may be a metal plate or a metal foil. Examples of the material of the metal sheet include aluminum and copper.
  • FIG. 4 is a cross-sectional view showing an example of a laminate.
  • FIG. 4 shows a cross section of the laminate 20 cut along the lamination direction.
  • the laminate 20 includes the composite sheet 10 described above and metal sheets 22 laminated on a pair of main surfaces (two main surfaces) of the composite sheet 10 .
  • the material and thickness of the plurality of metal sheets 22 may be the same or different. Also, it is not essential to provide the metal sheets 22 on both major surfaces of the composite sheet 10 . In a variant, only one major surface of composite sheet 10 may be provided with metal sheet 22 .
  • the metal sheet 22 in the laminate 20 is in contact with the composite sheet 10. Thereby, the metal sheet 22 and the composite sheet 10 are adhered with high adhesion. In order to fix this state, the composite sheet 10 may be cured and the two may be joined together with a cured resin. Since the metal sheet 22 and the composite sheet 10 are adhered to each other with high adhesion, the laminated body 20 can be suitably used as a heat dissipation member, for example, in a semiconductor device or the like.
  • the thickness of the laminate 20 may be, for example, less than 12.0 mm, less than 6.0 mm, or less than 3.0 mm.
  • the lower limit of the thickness of the laminate 20 may be, for example, 0.6 mm or more.
  • the laminated body 20 can be sufficiently miniaturized.
  • Such a laminate 20 is suitably used as a component of a semiconductor device, for example.
  • the thickness of the laminate 20 may be adjusted within the ranges described above, and may be, for example, 0.6-12.0 mm, or 0.6-6.0 mm.
  • the laminate 20 includes the composite sheet 10, it is possible to achieve both high levels of thermal conductivity and insulation reliability. For example, by increasing the curing rate of the resin in the cured region in advance, the outflow of the resin when forming the laminate is sufficiently suppressed, and the expected insulation properties of the composite sheet 10 can be sufficiently exhibited. .
  • the above-mentioned composite sheet can be produced, for example, by impregnating the nitride sintered plate with a resin and then subjecting the region including the outer periphery to multiple hardening treatments (manufacturing method A), the outer periphery of the nitride sintered plate Only the resin is impregnated and cured or semi-cured, and then the resin is further impregnated and the whole is cured or semi-cured in the same manner.
  • Production method A is desirable from the viewpoint of facilitating adjustment of the range of the cured region.
  • One embodiment of the method for producing a composite sheet includes an impregnation step of impregnating a porous nitride sintered plate with a resin composition to obtain a resin-impregnated sheet, and heating the resin-impregnated sheet to a mechanism.
  • a nitride sintered plate prepared in advance may be used as the porous nitride sintered plate, or a nitride sintered plate prepared by the following sintering process may be used.
  • a nitride sintered plate prepared by the following sintering process may be used.
  • the sintering step described later can be omitted.
  • a raw material powder containing nitride is prepared.
  • the nitride contained in the raw material powder may contain, for example, at least one nitride selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride.
  • the boron nitride may be amorphous boron nitride or hexagonal boron nitride.
  • the raw material powder is, for example, an amorphous boron nitride powder having an average particle size of 0.5 to 10 ⁇ m, or an average particle size of 3.0 to 40 ⁇ m. Certain hexagonal boron nitride powders can be used.
  • a compound containing nitride powder may be molded and sintered to obtain a nitride sintered body.
  • the molding may be carried out, for example, by uniaxial pressing or cold isostatic pressing (CIP).
  • a sintering aid may be blended into the formulation prior to molding.
  • sintering aids include metal oxides such as yttrium oxide, aluminum oxide and magnesium oxide, alkali metal carbonates such as lithium carbonate and sodium carbonate, and boric acid.
  • the amount of the sintering aid is, for example, 0.01 parts by mass or more, or 0.1 parts per 100 parts by mass of the total of the nitride and the sintering aid.
  • the compounding amount of the sintering aid may be, for example, 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less with respect to a total of 100 parts by mass of the nitride and the sintering aid.
  • the amount of the sintering aid may be adjusted within the above range, for example, 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, relative to the total 100 parts by mass of the nitride and the sintering aid. It may be parts by mass.
  • the compound may be formed into a sheet-like molded body by, for example, a doctor blade method.
  • the molding method is not particularly limited, and press molding may be performed using a mold to form a molded body.
  • the molding pressure may be, for example, 5-350 MPa.
  • the shape of the compact may be a sheet with a thickness of less than 2 mm. If a nitride sintered plate is produced using such a sheet-like compact, a sheet-like composite having a thickness of less than 2 mm can be produced without cutting the nitride sintered plate.
  • the material loss due to processing can be reduced by forming the block into a sheet from the compact stage. Therefore, the composite can be manufactured with high yield.
  • the sintering temperature in the sintering step may be, for example, 1600°C or higher, or 1700°C or higher.
  • the sintering temperature may be, for example, 2200° C. or lower, or 2000° C. or lower.
  • the sintering time may be, for example, 1 hour or more and may be 30 hours or less.
  • the atmosphere during sintering may be, for example, an inert gas atmosphere such as nitrogen, helium, and argon.
  • a batch type furnace and a continuous type furnace can be used.
  • Batch type furnaces include, for example, muffle furnaces, tubular furnaces, atmosphere furnaces, and the like.
  • continuous furnaces include rotary kilns, screw conveyor furnaces, tunnel furnaces, belt furnaces, pusher furnaces, and large continuous furnaces.
  • a nitride sintered body or a nitride sintered plate can be obtained.
  • the nitride sintered body may be block-shaped.
  • a cutting step may be performed to process it so that it has a thickness of less than 2 mm.
  • the nitride sintered body is cut using, for example, a wire saw.
  • the wire saw may be, for example, a multi-cut wire saw or the like.
  • a sheet-like nitride sintered plate having a thickness of less than 2 mm, for example, can be obtained by such a cutting process. Thereby, the nitride sintered plate can be smoothly impregnated with the resin composition in the next impregnation step.
  • the pores of the nitride sintered body are impregnated with a resin composition having a viscosity of 10 to 500 mPa ⁇ s to obtain a resin-impregnated body.
  • a resin composition having a viscosity of 10 to 500 mPa ⁇ s By reducing the thickness of the nitride sintered body, impregnation of the resin composition can be facilitated. Also, by setting the viscosity of the resin composition to a range suitable for impregnation, the filling rate of the resin in the resin-impregnated body can be sufficiently increased.
  • the viscosity of the resin composition when the nitride sintered plate is impregnated with the resin composition may be, for example, 440 mPa ⁇ s or less, 390 mPa ⁇ s or less, or 340 mPa ⁇ s or less. By lowering the viscosity of the resin composition in this way, the impregnation of the resin composition can be sufficiently promoted.
  • the viscosity of the resin composition when the nitride sintered plate is impregnated with the resin composition may be, for example, 15 mPa ⁇ s or more, or 20 mPa ⁇ s or more.
  • the viscosity of the resin composition may be adjusted by partially polymerizing the monomer component, or may be adjusted by adding a solvent.
  • the viscosity of the resin composition when the nitride sintered plate is impregnated with the resin composition may be adjusted within the above range, and may be, for example, 15 to 440 mPa ⁇ s or 20 to 340 mPa ⁇ s.
  • the above viscosity of the resin composition is the viscosity at the temperature (T1) of the resin composition when the nitride sintered plate is impregnated with the resin composition.
  • This viscosity is a value measured using a rotational viscometer at a shear rate of 10 (1/sec) and a temperature (T1). Therefore, by changing the temperature T1, the viscosity at which the nitride sintered plate is impregnated with the resin composition may be adjusted.
  • the temperature (T2) may be, for example, 80-140°C.
  • Impregnation of the nitride sintered plate with the resin composition may be performed under pressure or under reduced pressure.
  • the impregnation method is not particularly limited, and the nitride sintered plate may be immersed in the resin composition, or the surface of the nitride sintered plate may be coated with the resin composition.
  • the impregnation step may be performed under either reduced pressure or increased pressure, or a combination of impregnation under reduced pressure and increased pressure.
  • the pressure in the impregnation device when the impregnation step is performed under reduced pressure conditions may be, for example, 1000 Pa or less, 500 Pa or less, 100 Pa or less, 50 Pa or less, or 20 Pa or less.
  • the pressure in the impregnation device when the impregnation step is performed under pressurized conditions may be, for example, 1 MPa or higher, 3 MPa or higher, 10 MPa or higher, or 30 MPa or higher.
  • the impregnation of the resin composition by capillary action may be promoted, and the resin filling rate in the resin-impregnated body may be adjusted.
  • the median pore diameter of the nitride sintered plate may be, for example, 0.3-6.0 ⁇ m, 0.5-5.0 ⁇ m, or 1.0-4.0 ⁇ m.
  • the resin composition it is possible to use, for example, one that becomes the resin mentioned in the explanation of the above composite by curing or semi-curing reaction.
  • the resin composition may contain a solvent.
  • Solvents include, for example, ethanol and aliphatic alcohols such as isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol, 2-(2-methoxy Ether alcohols such as ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, acetone, methyl ethyl ketone, methyl isobutyl Ketones, ketones such as diisobutyl ketone, and aromatic hydrocarbons such as toluene and xylene.
  • solvents include, for example, ethanol and aliphatic alcohols such as isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol
  • the resin composition is thermosetting and comprises, for example, at least one compound selected from the group consisting of a compound having a cyanate group, a compound having a bismaleimide group, and a compound having an epoxy group, and a curing agent. may contain.
  • Examples of compounds having a cyanate group include dimethylmethylenebis(1,4-phenylene)biscyanate and bis(4-cyanatophenyl)methane.
  • Dimethylmethylenebis(1,4-phenylene)biscyanate is commercially available, for example, as TACN (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name).
  • Examples of compounds having a bismaleimide group include N,N'-[(1-methylethylidene)bis[(p-phenylene)oxy(p-phenylene)]]bismaleimide and 4,4'-diphenylmethanebismaleimide. etc.
  • N,N'-[(1-methylethylidene)bis[(p-phenylene)oxy(p-phenylene)]]bismaleimide is commercially available as BMI-80 (manufactured by K.I. Kasei Co., Ltd., trade name), for example. readily available.
  • Examples of compounds having epoxy groups include bisphenol F type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, and polyfunctional epoxy resins.
  • it may be 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene, which is commercially available as HP-4032D (manufactured by DIC Corporation, trade name).
  • the curing agent may contain a phosphine-based curing agent and an imidazole-based curing agent.
  • a phosphine-based curing agent can promote a triazine formation reaction by trimerization of a compound having a cyanate group or a cyanate resin.
  • Phosphine-based curing agents include, for example, tetraphenylphosphonium tetra-p-tolylborate and tetraphenylphosphonium tetraphenylborate. Tetraphenylphosphonium tetra-p-tolylborate is commercially available, for example, as TPP-MK (manufactured by Hokko Chemical Industry Co., Ltd., trade name).
  • the imidazole-based curing agent generates oxazoline and accelerates the curing reaction of the epoxy group-containing compound or epoxy resin.
  • imidazole curing agents include 1-(1-cyanomethyl)-2-ethyl-4-methyl-1H-imidazole and 2-ethyl-4-methylimidazole.
  • 1-(1-Cyanomethyl)-2-ethyl-4-methyl-1H-imidazole is commercially available, for example, as 2E4MZ-CN (manufactured by Shikoku Kasei Co., Ltd., trade name).
  • the content of the phosphine-based curing agent is, for example, 5 parts by mass or less, 4 parts by mass or less, or 3 parts by mass with respect to 100 parts by mass of the total amount of the compound having a cyanate group, the compound having a bismaleimide group, and the compound having an epoxy group. It may be less than or equal to parts by mass.
  • the content of the phosphine-based curing agent is, for example, 0.1 parts by mass or more or 0.5 parts by mass with respect to 100 parts by mass of the total amount of the compound having a cyanate group, the compound having a bismaleimide group, and the compound having an epoxy group. It may be more than part.
  • the content of the phosphine-based curing agent may be adjusted within the above-mentioned range, and for example, 0.5 parts per 100 parts by mass of the total amount of the compound having a cyanate group, the compound having a bismaleimide group and the compound having an epoxy group. It may be 1 to 5 parts by mass.
  • the content of the imidazole-based curing agent is, for example, 0.1 parts by mass or less, 0.05 parts by mass with respect to 100 parts by mass of the total amount of the compound having a cyanate group, the compound having a bismaleimide group, and the compound having an epoxy group. parts or less or 0.03 parts by mass or less.
  • the content of the imidazole-based curing agent is, for example, 0.001 parts by mass or more or 0.005 parts by mass with respect to 100 parts by mass of the total amount of the compound having a cyanate group, the compound having a bismaleimide group, and the compound having an epoxy group. It may be more than part.
  • the content of the imidazole-based curing agent may be adjusted within the range described above. 001 to 0.1 parts by mass.
  • the resin composition may contain other components apart from the main agent and curing agent.
  • Other components include, for example, other resins such as phenolic resins, melamine resins, urea resins, and alkyd resins, silane coupling agents, leveling agents, antifoaming agents, surface control agents, and wetting and dispersing agents. It's okay.
  • the content of these other components may be, for example, 20% by mass or less, 10% by mass or less, or 5% by mass or less based on the total amount of the resin composition.
  • the resin composition in the resin-impregnated body obtained by the impregnation step is semi-cured.
  • the resin composition is semi-cured by heating and/or light irradiation to prepare a resin-impregnated sheet. .
  • the heating temperature for semi-curing the resin composition by heating may be, for example, 80 to 130°C.
  • the semi-cured resin obtained by semi-curing the resin composition may contain, as a resin component, at least one thermosetting resin selected from the group consisting of cyanate resins, bismaleimide resins, and epoxy resins.
  • the semi-cured resin may also contain a curing agent.
  • semi-cured resins include other resins such as phenolic resins, melamine resins, urea resins, and alkyd resins, as well as silane coupling agents, leveling agents, antifoaming agents, surface control agents, and components derived from wetting and dispersing agents.
  • the resin composition is cured, semi-cured, or semi-cured by irradiating a region including the outer periphery of the resin-impregnated sheet obtained through the first curing step with heat or laser light.
  • a composite sheet as described above is prepared by curing the resin. The region irradiated with heat or laser light is exposed to multiple curing treatments, and the curing rate of the resin is higher than that of other regions.
  • the method of heating or irradiating the predetermined region of the resin-impregnated sheet with laser is not particularly limited. For example, laser light may be partially irradiated using a mask.
  • the second curing step when curing or semi-curing the resin composition and curing the semi-cured resin by heat, for example, a method of partially heat-treating at a temperature higher than that in the first curing step, or A method of performing heat treatment at the same heating temperature as in the first curing step can be used only for the predetermined region described above.
  • the resin composition when the resin composition is cured or semi-cured and the semi-cured resin is cured by laser light, for example, a method of irradiating only the predetermined region with ultraviolet light or the like can be used. .
  • the semi-cured resin obtained by semi-curing the resin composition and the resin obtained by curing the semi-cured resin are heated by at least one selected from the group consisting of cyanate resins, bismaleimide resins, and epoxy resins as a resin component. It may contain a curable resin.
  • the semi-cured resin and resin may also contain a curing agent.
  • semi-cured resins and resins include other resins such as phenolic resins, melamine resins, urea resins, and alkyd resins, as well as silane coupling agents, leveling agents, antifoaming agents, and surface conditioning agents. It may contain ingredients derived from agents, wetting and dispersing agents, and the like.
  • the first curing step and the second curing step are preferably carried out in a situation where the resin composition exists around the resin-impregnated body.
  • the resin composition is supplied from the periphery of the resin-impregnated body, and it is possible to further suppress the formation of voids.
  • the existence of the similar resin in the surroundings can also suppress the generation of voids.
  • the above-described manufacturing method may have other steps such as the sintering step, the impregnation step, the first hardening step and the second hardening step.
  • Other steps include, for example, a step of removing impurities from the sintered body by drawing a vacuum before the impregnation step.
  • One embodiment of the composite sheet manufacturing method is a first impregnation step of impregnating a region including the outer periphery of a porous nitride sintered plate with a first resin composition to obtain a first resin-impregnated sheet. and a first curing step of heating the first resin-impregnated sheet and curing or semi-curing the first resin composition filled in the pores to obtain a first resin-filled sheet containing a resin in a region including the outer peripheral edge. a second impregnation step of impregnating the first resin-filled sheet with the second resin composition to obtain a second resin-impregnated sheet; and heating the second resin-impregnated sheet to cure the second resin composition.
  • the region including the outer edge of the nitride sintered plate is impregnated with the first resin composition.
  • adjustment is made so that other regions of the nitride sintered plate are not impregnated with the first resin composition.
  • only the region including the outer periphery of the nitride sintered plate may be immersed in the melt or solution of the first resin composition to impregnate the first resin composition, and the nitride sintered plate
  • the first resin composition may be impregnated by applying the melt or solution of the first resin composition only to the region including the outer periphery.
  • the first curing step by semi-curing or curing the first resin composition impregnated in the first impregnation step, only the region including the outer periphery of the nitride sintered plate is filled with the semi-cured resin or resin. 1 Prepare a resin-filled sheet.
  • the method for semi-curing or curing the first resin composition may be heating and/or light irradiation, and may be the same as those described in the above manufacturing method.
  • the first resin-filled sheet obtained through the first impregnation step and the first curing step is impregnated with the second resin composition.
  • the first resin-filled sheet may be immersed in a melt or solution of the second resin composition to be impregnated with the second resin composition, and the first resin-filled sheet may be impregnated with the second resin composition. may be applied as a melt or solution of
  • the second resin-impregnated sheet obtained in the second impregnation step is cured or semi-cured.
  • the region where the resin composition has been cured or semi-cured in the first curing step is also heated and/or irradiated with light again.
  • the hardening rate of the resin in the containing region is higher than in other regions.
  • the viscosities at which the first resin composition and the second resin composition are impregnated may be the same or different, and both may be the same as those described in the manufacturing method above.
  • One embodiment of the composite sheet manufacturing method includes an impregnation step of impregnating a porous nitride sintered plate with a resin composition to obtain a resin-impregnated sheet, and heating the resin-impregnated sheet to form pores.
  • the curing rate of the third resin is higher than the curing rate of the first resin.
  • the steps up to the impregnation step are the same as those of the manufacturing method A. Differences from the above manufacturing method (manufacturing method A) will be described below.
  • the resin-filled sheet is obtained by heating the entire resin-impregnated sheet and curing or semi-curing the resin composition. At this time, it is not necessary to specify the heating region as in the above manufacturing method (manufacturing method A). Since the resin composition and the like exemplified in the production method (production method A) described above can be used, the curing conditions shown in production method A can be applied accordingly.
  • a resin-filled sheet that has been prepared in advance may be used, and in this case, the sintering process, the impregnation process, and the curing process may be omitted.
  • a resin layer containing the third resin is provided on the side surface of the resin-filled sheet to suppress the outflow of the first resin. It is desirable that the third resin be provided continuously over the entire side surface of the resin-filled sheet, but from the viewpoint of suppressing the outflow of the first resin, it may be provided on at least a part of the side surface of the filled resin sheet. , may be discontinuously formed.
  • the third resin may be a semi-cured resin obtained by semi-curing the resin composition and a resin obtained by curing the semi-cured resin.
  • a resin component of the third resin at least one thermosetting resin selected from the group consisting of cyanate resins, bismaleimide resins, and epoxy resins may be contained.
  • the semi-cured resin and resin may also contain a curing agent.
  • semi-cured resins and resins include other resins such as phenolic resins, melamine resins, urea resins, and alkyd resins, as well as silane coupling agents, leveling agents, antifoaming agents, and surface conditioning agents. It may contain ingredients derived from agents, wetting and dispersing agents, and the like.
  • the constituent components of the first resin and the third resin may be the same or different.
  • An embodiment of a method for manufacturing a laminate has a lamination step of laminating the composite sheet and the metal sheet described above, and heating and pressurizing them.
  • the composite sheet a composite sheet obtained by any of the manufacturing methods described above can be used. That is, the manufacturing method of the laminate may be a manufacturing method including the above-described lamination step in addition to the manufacturing method described above.
  • the metal sheet may be a metal plate or a metal foil.
  • a metal sheet is placed on the main surface of the composite sheet. With the main surfaces of the composite sheet and the metal sheet in contact with each other, pressure is applied in the direction in which the main surfaces face each other, and heating is performed. Note that the pressurization and heating need not necessarily be performed at the same time, and the heating may be performed after pressurization and crimping.
  • the laminate thus obtained can be used for manufacturing semiconductor devices and the like.
  • a semiconductor element may be provided on one of the metal sheets.
  • the other metal sheet may be joined with cooling fins.
  • Example 1 [Production of nitride sintered plate] 100 parts by mass of orthoboric acid manufactured by Shin Nippon Denko Co., Ltd. and 35 parts by mass of acetylene black (trade name: HS100) manufactured by Denka Co., Ltd. were mixed using a Henschel mixer. The obtained mixture was filled in a graphite crucible and heated at 2200° C. for 5 hours in an argon atmosphere in an arc furnace to obtain massive boron carbide (B 4 C). The resulting mass was coarsely pulverized with a jaw crusher to obtain coarse powder. This coarse powder was further pulverized by a ball mill having silicon carbide balls ( ⁇ 10 mm) to obtain pulverized powder.
  • HS100 acetylene black
  • the prepared pulverized powder was filled in a crucible made of boron nitride. After that, using a resistance heating furnace, heating was performed for 10 hours under conditions of 2000° C. and 0.85 MPa in a nitrogen gas atmosphere. Thus, a fired product containing boron carbonitride (B 4 CN 4 ) was obtained.
  • a sintering aid was prepared by blending powdered boric acid and calcium carbonate. In preparation, 50.0 parts by mass of calcium carbonate was blended with 100 parts by mass of boric acid. At this time, the atomic ratio of boron to calcium was 17.5 atomic % of calcium to 100 atomic % of boron. 20 parts by mass of a sintering aid was blended with 100 parts by mass of the fired product, and mixed using a Henschel mixer to prepare a powdery compound.
  • the compact was placed in a boron nitride container and introduced into a batch-type high-frequency furnace. In a batch-type high-frequency furnace, heating was performed for 5 hours under the conditions of atmospheric pressure, nitrogen flow rate of 5 L/min, and 2000°C. After that, the boron nitride sintered body was taken out from the boron nitride container. Thus, a sheet-like (square prism-like) boron nitride sintered body was obtained. The thickness of the boron nitride sintered plate was 0.36 mm.
  • the resin composition remaining on the upper main surface of the boron nitride sintered body was smoothed using a stainless steel scraper (manufactured by Narby Co., Ltd.). An excess resin composition was removed to obtain a resin-impregnated body having a smooth main surface.
  • the cure rate of the resin impregnated into the composite sheet was determined by measurement using a differential scanning calorimeter.
  • the calorific value Q per unit mass generated when 2 mg of the uncured resin composition was completely cured was measured.
  • a 10 mg sample taken from the semi-cured material of the composite was heated in the same manner, and the amount of heat generated per unit mass R generated when completely cured was determined.
  • the mass of the sample used for the measurement with the differential scanning calorimeter was the same as that of the resin composition used for the measurement of the calorific value Q.
  • the curing rate of the resin composition impregnated in the composite was determined by the following formula (A).
  • the curing rate of the resin in the cured region was 85%, and the curing rate of the resin in the other regions was 32%.
  • the sample collection site from the cured region is 15 mm in the direction perpendicular to the direction of the total length L of the composite sheet 10 in the cured region 14 of the composite sheet 10, and the direction of the total length L is 15 mm.
  • a region of 1 mm in the horizontal direction was cut out and used. For other regions, samples of the same size as above were cut out from the central portion of the composite sheet and used.
  • the bulk density of the boron nitride sintered plate and composite sheet conforms to JIS Z 8807:2012 "Method for measuring density and specific gravity by geometric measurement", and the length of each side of the boron nitride sintered plate or composite sheet (measured with vernier calipers) and the mass of the boron nitride sintered plate or composite sheet measured with an electronic balance (see JIS Z 8807:2012, Item 9).
  • the theoretical density of the composite sheet was determined by the following formula (4).
  • Theoretical density of composite sheet bulk density of boron nitride sintered plate + true density of resin ⁇ (1 - bulk density of boron nitride sintered plate / true density of boron nitride) (4)
  • the true density of the boron nitride sintered plate and resin is measured using a dry automatic densitometer in accordance with JIS Z 8807:2012 "Method for measuring density and specific gravity by gas replacement method". It was determined from the volume and mass of (see JIS Z 8807:2012, item 11, formulas (14) to (17)).
  • etching resist agent was screen-printed on one surface of the obtained laminate so as to form a circular shape with a diameter of 20 mm, and an etching resist agent was screen-printed on the entire surface of the laminate structure on the other surface. After printing, the etching resist agent was irradiated with ultraviolet rays to be cured to form a resist.
  • the copper plate on which the circular resist was formed was etched with a cupric chloride solution to form a circular copper circuit with a diameter of 20 mm on one surface of the laminate.
  • the laminated structure having a circular copper circuit formed thereon was obtained, which was the object to be measured.
  • the dielectric breakdown voltage of the obtained laminated structure was measured according to JIS C2110-1:2016 using a withstand voltage tester (manufactured by Kikusui Denshi Kogyo Co., Ltd., device name: TOS-8700). Table 1 shows the results.
  • Example 2 [Preparation of resin-impregnated body] 80 parts by mass of a compound having a cyanate group, 20 parts by mass of a compound having a bismaleimide group, and 50 parts by mass of a compound having an epoxy group were weighed into a container, and the total amount of the above three compounds was 100 parts by mass. 1 part by mass of a phosphine-based curing agent and 0.01 part by mass of an imidazole-based curing agent were added and mixed. Since the epoxy resin was in a solid state at room temperature, it was mixed while being heated to about 80°C. The resulting thermosetting composition had a viscosity of 10 mPa ⁇ sec at 100°C.
  • the prepared resin composition was heated to 100° C., it was dropped onto the upper main surface of the boron nitride sintered body using a dispenser while maintaining the temperature to impregnate the resin composition.
  • the amount of the resin composition dropped was 1.5 times the total volume of the pores of the boron nitride sintered body. Part of the resin composition remained on the main surface without impregnating the boron nitride sintered body.
  • thermosetting composition The following compounds were used to prepare the thermosetting composition.
  • Phosphine-based curing agent tetraphenylphosphonium tetra-p-tolylborate (manufactured by Chemical Co., Ltd., trade name: TPP-MK)
  • Imidazole-based curing agent 1-(1-cyanomethyl)-2-ethyl-4-methyl-1H-imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: 2E4MZ-CN)
  • the resin composition remaining on the upper main surface of the boron nitride sintered body was smoothed using a stainless steel scraper (manufactured by Narby Co., Ltd.). An excess resin composition was removed to obtain a resin-impregnated body having a smooth main surface.
  • Example 2 A composite and a laminate were prepared by the same procedure as in Example 2, except that the region including the peripheral edge of the resin-impregnated body was not subjected to additional heat treatment.
  • Example 2 and Comparative Examples 1 and 2 For the composite sheets and laminates prepared in Example 2 and Comparative Examples 1 and 2, the width of the cured region, the curing rate of the resin in the cured region and other regions, and the resin filling rate were measured in the same manner as in Example 1. did.
  • the laminates prepared in Example 2 and Comparative Examples 1 and 2 were evaluated for adhesive strength and dielectric breakdown voltage. Table 1 shows the results.
  • the present disclosure it is possible to provide a composite sheet that has excellent adhesion to an adherend and can exhibit excellent insulating properties after being adhered to an adherend. According to the present disclosure, it is also possible to provide a laminate having excellent insulating properties and a method for manufacturing the same.

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  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
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Abstract

Selon un aspect, la présente divulgation concerne une feuille composite comprenant : une plaque frittée de nitrure poreux ; et une résine chargée dans des trous d'air de la plaque frittée de nitrure. La feuille composite a une région de durcissement comprenant un de ses bords périphériques externes, et un rapport de durcissement de la résine dans la région de durcissement est supérieur à celui de la résine dans d'autres régions.
PCT/JP2022/005177 2021-03-31 2022-02-09 Feuille composite et son procédé de fabrication, et stratifié et son procédé de fabrication Ceased WO2022209335A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2008073875A (ja) * 2006-09-19 2008-04-03 Toray Ind Inc Ｆｒｐ成形体の製造方法およびその成形体。
WO2015022956A1 (fr) * 2013-08-14 2015-02-19 電気化学工業株式会社 Substrat de circuit composite nitrure de bore - résine, et substrat de circuit à dissipateur thermique composite nitrure de bore - résine intégré
WO2017155110A1 (fr) * 2016-03-10 2017-09-14 デンカ株式会社 Corps composite de résine céramique
WO2019111978A1 (fr) * 2017-12-05 2019-06-13 デンカ株式会社 Corps composite de résine céramique de nitrure
WO2019172345A1 (fr) * 2018-03-07 2019-09-12 デンカ株式会社 Corps temporairement lié à base d'un corps composite céramique - résine et d'une plaque métallique ainsi que procédé de fabrication de celui-ci, corps de transport contenant ce corps temporairement lié, et procédé de transport associé
WO2020203586A1 (fr) * 2019-03-29 2020-10-08 デンカ株式会社 Composite, procédé de production de composite, stratifié et procédé de production de stratifié

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008073875A (ja) * 2006-09-19 2008-04-03 Toray Ind Inc Ｆｒｐ成形体の製造方法およびその成形体。
WO2015022956A1 (fr) * 2013-08-14 2015-02-19 電気化学工業株式会社 Substrat de circuit composite nitrure de bore - résine, et substrat de circuit à dissipateur thermique composite nitrure de bore - résine intégré
WO2017155110A1 (fr) * 2016-03-10 2017-09-14 デンカ株式会社 Corps composite de résine céramique
WO2019111978A1 (fr) * 2017-12-05 2019-06-13 デンカ株式会社 Corps composite de résine céramique de nitrure
WO2019172345A1 (fr) * 2018-03-07 2019-09-12 デンカ株式会社 Corps temporairement lié à base d'un corps composite céramique - résine et d'une plaque métallique ainsi que procédé de fabrication de celui-ci, corps de transport contenant ce corps temporairement lié, et procédé de transport associé
WO2020203586A1 (fr) * 2019-03-29 2020-10-08 デンカ株式会社 Composite, procédé de production de composite, stratifié et procédé de production de stratifié

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