WO2023162705A1 - Feuille composite et stratifié - Google Patents
Feuille composite et stratifié Download PDFInfo
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- WO2023162705A1 WO2023162705A1 PCT/JP2023/004440 JP2023004440W WO2023162705A1 WO 2023162705 A1 WO2023162705 A1 WO 2023162705A1 JP 2023004440 W JP2023004440 W JP 2023004440W WO 2023162705 A1 WO2023162705 A1 WO 2023162705A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin
- semi
- composite sheet
- plate
- cured
- Prior art date
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Images
Classifications
-
- 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
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
-
- 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
-
- 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 composite sheets and laminates.
- Components such as power devices, transistors, thyristors, and CPUs are required to efficiently dissipate the heat generated during use.
- a composite sheet composed of ceramics such as boron nitride and resin is used as a heat dissipation member for such an insulating layer and thermal interface material.
- a composite sheet in which a porous ceramic sintered plate (for example, a boron nitride sintered plate) is impregnated with a resin is being studied (see, for example, Patent Document 1). Further, in a laminated substrate having a circuit board and a resin-impregnated boron nitride sintered plate, the primary particles constituting the boron nitride sintered plate and the circuit board are brought into direct contact to reduce the thermal resistance of the laminated substrate and improve heat dissipation. is also being studied (see Patent Document 2, for example).
- the adherend such as the circuit board and the composite described above stronger.
- the surface roughness of the adherend is large, for example, when the surface roughness Rz is 20 ⁇ m or more, sufficient adhesion may not be achieved.
- An object of the present disclosure is to provide a composite sheet that can exhibit sufficient adhesion to an adherend even when the surface roughness of the adherend is relatively large.
- the present disclosure also aims to provide laminates prepared using the composite sheets described above.
- the present disclosure provides the following [1] to [8].
- A/B Composite sheet, which is 0.5 to 1.7.
- the resin layer has a peel adhesion strength of 5 N/cm when peeled at 90 degrees, which is measured based on the peel adhesion strength test specified in JIS K 6854: 1999 when adhered to a copper plate.
- the composite sheet according to [1], which is a layer exceeding [3] The composite sheet according to [1] or [2], wherein the resin-filled plate has a thickness of 2.0 mm or less.
- [5] The composite sheet according to any one of [1] to [4], wherein the nitride sintered plate has a porosity of 40 to 65% by volume.
- [6] The composite sheet according to any one of [1] to [5], wherein the nitride sintered plate has a median pore diameter of 1.5 to 4.0 ⁇ m.
- [7] comprising an insulating sheet and a metal sheet provided on at least one main surface of the insulating sheet, A laminate, wherein the insulating sheet is a cured product of the composite sheet according to any one of [1] to [6].
- [8] The laminate according to [7], wherein the main surface of the metal sheet on the insulating sheet side has a surface roughness Rz of 20 ⁇ m or more.
- One aspect of the present disclosure is a resin-filled plate including a porous nitride sintered plate and a first semi-cured resin filled in the pores of the nitride sintered plate; A resin layer containing a second semi-cured resin provided on at least a part of the surface, and A is the amount of heat generated due to curing of the first semi-cured resin, which is measured by a differential scanning calorimeter; Provided is a composite sheet having a value of A/B of 0.5 to 1.7, where B is the amount of heat generated upon curing of the second semi-cured resin.
- the composite sheet includes a resin layer containing a semi-cured resin in addition to the resin-filled plate, it can be deformed following minute irregularities on the surface of the adherend when it is joined to the adherend. Also, the ratio of the calorific value measured by the differential scanning calorimeter of the first semi-cured resin and the second semi-cured resin is adjusted to be within a predetermined range, so that the adherend Even if the surface roughness of is relatively large, it can exhibit sufficient adhesiveness to the adherend.
- the fact that the above-mentioned calorific value ratio (A/B value) is within a predetermined range means that the first semi-cured resin and the second semi-cured resin It can be used as an index for measuring the degree of progress of polymerization.
- the resin layer When the resin layer is adhered to a copper plate, it is measured based on the peel strength test specified in JIS K 6854: 1999, and the layer has a peel strength of more than 5 N/cm when peeled off at 90 degrees. can be Since the resin layer has a peel strength within the above range as the peel strength measured by the test described above, the adhesion between the resin layer and the adherend exhibits more sufficient adhesion. can.
- the thickness of the resin-filled plate may be 2.0 mm or less.
- the thickness of the resin layer may be 2 to 50 ⁇ m.
- the thickness of the resin layer is within the above range, even if the surface roughness of the bonding surface of the adherend is large, the resin can penetrate and firmly bond, and curing after bonding is possible. It is possible to further suppress deterioration in heat dissipation due to excessive thickness of the resin layer.
- the porosity of the nitride sintered plate may be 40 to 65% by volume.
- the median pore size of the nitride sintered plate may be 1.5 to 4.0 ⁇ m.
- One aspect of the present disclosure provides a laminate comprising an insulating sheet and a metal sheet provided on at least one main surface of the insulating sheet, wherein the insulating sheet is a cured product of the composite sheet described above. do.
- the laminate is obtained by bonding the composite sheet to the metal sheet, the adhesion between the metal sheet and the cured product of the composite sheet can be excellent.
- the laminate may have a surface roughness Rz of 20 ⁇ m or more on the main surface of the metal sheet on the insulating sheet side. Since the laminate is obtained by laminating the above-mentioned composite sheet with a metal sheet and then curing the laminate, even if the surface roughness of the metal sheet is large, the laminate can be sufficiently strongly bonded.
- the present disclosure it is possible to provide a composite sheet that can exhibit sufficient adhesiveness to an adherend even when the surface roughness of the adherend is relatively large.
- the present disclosure can also provide laminates prepared using the composite sheets described above.
- 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 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 resin-filled plate containing a porous nitride sintered plate, a first semi-cured resin filled in the pores of the nitride sintered plate, and the resin-filled plate. and a resin layer containing a second semi-cured resin provided on at least a portion of the main surface.
- A is the amount of heat generated due to curing of the first semi-cured resin
- B is the amount of heat generated due to curing of the second semi-cured resin, as measured by a differential scanning calorimeter
- a /B has a value of 0.5 to 1.7.
- 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.
- the composite sheet 10 has a resin-filled plate 12 and resin layers 14 provided on both main surfaces of a pair of main surfaces 12 a of the resin-filled plate 12 .
- FIG. 1 shows an example in which the composite sheet 10 is provided with the resin layer 14 so as to cover the entire main surface 12a of the resin-filled plate 12. 14 may be provided on at least part of the resin-filled plate 12 . However, when the resin layer 14 is partially provided, it is preferably provided in the center so as not to entrap gas or the like when it comes into contact with the adherend.
- the resin layer 14 may be provided so as to be smaller than the area of the main surface 12 a of the resin-filled plate 12 .
- the composite sheet 10 is shown as an example in which the resin layer 14 is provided on both main surfaces 12a of the resin-filled plate 12, depending on the adhesion of the resin-filled plate 12, even one of the main surfaces may good.
- the composite sheet 10 may further have a resin layer on the side surface of the resin-filled plate 12 .
- the thickness of the composite sheet 10 may be, for example, less than 8.0 mm, less than 5.0 mm, or less than 3.0 mm.
- the lower limit of the thickness of the composite sheet 10 may be, for example, 0.1 mm or more, 0.3 mm or more, or 0.5 mm or more. This allows the composite sheet 10 to be sufficiently miniaturized.
- the thickness of the composite sheet 10 may be adjusted within the above range depending on the application, and may be, for example, 0.1 mm or more and less than 8.0 mm.
- Such a composite sheet 10 is suitably used as a component of a semiconductor device, for example.
- 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 main surface 12a of the resin-filled plate 12 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.
- the size of the main surface 12a of the resin-filled plate 12 may be, for example, 250000 mm 2 or less, or 150000 mm 2 or less.
- the sizes of the pair of main surfaces 12a of the resin-filled plate 12 are generally the same, but they do not need to be exactly the same, and may be different from each other.
- the volume ratio of the first semi-cured resin in the resin-filled plate 12 may be, for example, 40-65% by volume, 45-60% by volume, or 45-55% by volume, based on the total volume of the resin-filled plate 12. .
- the volume ratio of the nitride particles constituting the porous nitride sintered plate in the resin-filled plate 12 is, based on the total volume of the resin-filled plate 12, for example, 35 to 60% by volume, 40 to 55% by volume, or It may be 45-55% by volume.
- the resin-filled plate 12 having such a volume ratio can exhibit excellent strength.
- Examples of the porous nitride sintered plate forming the resin-filled plate 12 include a boron nitride sintered plate.
- 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, 4.0 ⁇ m or less, 3.8 ⁇ m or less, 3.6 ⁇ m or less, 3.4 ⁇ m or less, 3.2 ⁇ m or less, or 3.0 ⁇ 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, 1.5 ⁇ m or more, 1.6 ⁇ m or more, 1.7 ⁇ m or more, 1.8 ⁇ m or more, 1.9 ⁇ m or more, or 2.0 ⁇ m or more. . Since such a nitride sintered plate can be sufficiently deformed by pressurization during bonding, it can exhibit superior adhesion even when bonded to an adherend having a relatively large surface roughness.
- the median pore diameter of the pores of the nitride sintered plate may be adjusted within the range described above, and may be, for example, 1.5-4.0 ⁇ m, or 2.0-3.0 ⁇ m.
- the median pore diameter of the pores of the nitride sintered plate can be measured by the following procedure. First, the composite sheet is heated to remove the resin layer and the first semi-cured 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 upper limit of the porosity of the nitride sintered plate that is, the ratio of the volume of the pores in the nitride sintered plate may be, for example, 65% by volume or less, 60% by volume or less, or 58% by volume or less. .
- the upper limit of the porosity of the nitride sintered body is within the above range, it is possible to more sufficiently suppress the deterioration of the mechanical strength of the nitride sintered plate and to provide a composite sheet with excellent handleability.
- the lower limit of the porosity of the nitride sintered plate may be, for example, 40% by volume or more, 42% by volume or more, 44% by volume or more, or 45% by volume or more.
- the content of the first semi-cured resin can be increased, and the bonding with the resin layer can be further improved.
- the upper limit of the porosity of the nitride sintered body is within the above range, it is possible to impart appropriate flexibility to the resin-filled plate, so when bonding to an adherend having a relatively large surface roughness In addition, the resin-filled plate can be deformed, and the adhesion between the adherend and the composite sheet can be further improved.
- the porosity of the nitride sintered plate may be adjusted within the above range, and may be, for example, 40-65% by volume, or 40-60% by volume.
- the bulk density [Y (kg/m 3 )] is calculated from the volume and mass of the nitride sintered plate, and this bulk density and the theoretical density of the nitride [X (kg/m 3 )] 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 X is 2280 kg/m 3 .
- aluminum nitride the theoretical density X is 3260 kg/m 3 .
- silicon nitride the theoretical density X is 3170 kg/m 3 .
- Porosity (% by volume) [1-(Y/X)] x 100 (1)
- the bulk density Y may be from 800 to 1500 kg/m 3 and may be from 1000 to 1400 kg/m 3 . If the bulk density Y becomes too small, the strength of the nitride sintered plate tends to decrease. On the other hand, if the bulk density Y is too high, the amount of resin filled in the composite sheet is reduced, which may impair the good adhesiveness of the composite sheet.
- the thickness of the nitride sintered plate may be, for example, 5.0 mm or less, 3.0 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, 0.3 mm or more, or 0.5 mm or more.
- the thickness of the nitride sintered plate is measured along the direction perpendicular to the main surface, and if the thickness is not constant, select 10 arbitrary locations to measure the thickness, and the average value is the above may be within the range of The thickness of the nitride sintered plate corresponds to the thickness of the resin-filled plate.
- the first semi-cured resin contained in the resin-filled plate 12 is a semi-cured material (B stage) of a resin composition containing a main agent and a curing agent.
- 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 cured product (C stage) of the above-mentioned resin composition is one in which the curing reaction of the resin composition has progressed completely.
- the first semi-cured resin may contain a thermosetting resin or the like generated by the reaction of the main agent and the 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, for example, a differential scanning calorimeter that the resin contained in the composite sheet is a semi-cured product (B stage) before becoming a cured product (C stage).
- the upper limit of the curing rate of the first semi-cured resin contained in the resin-filled plate 12 may be, for example, 50% or less, 48% or less, 46% or less, 42% or less, 40% or less, or 38% or less. .
- the lower limit of the curing rate of the first semi-cured resin contained in the resin-filled plate 12 may be, for example, 20% or more, 23% or more, 25% or more, 30% or more, 33% or more, or 36% or more. .
- the curing rate of the first semi-cured resin may be adjusted within the above range, and may be, for example, 20-50%.
- the cure rate of the first semi-cured resin 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 of the first semi-cured resin from the resin-filled plate 12 is heated in the same manner, and the calorific value R per unit mass generated when the sample is completely cured is determined.
- the content c (% by mass) of the first semi-cured resin was determined by cross-sectional SEM image analysis and thermogravimetric differential thermal analysis (TG-DTA) of the resin-filled plate to be measured, and the determined first semi-cured
- the calorific value of the first semi-cured resin is calculated from the resin content and the calorific value R obtained by the above measurement.
- Examples of the first semi-cured resin include epoxy resin, cyanate resin, phenol resin, melamine resin, urea resin, bismaleimide resin, thermosetting polyimide, maleimide resin, maleimide-modified resin, silicone resin, silicone rubber, unsaturated polyester, At least one selected from the group consisting of polyurethane and alkyd resin may be included.
- the resin layer 14 is a layer that contains a second semi-cured resin and exhibits adhesiveness to the adherend. When the main surface of the adherend has fine irregularities, the resin layer 14 is deformed and can be impregnated with the second semi-cured resin in a semi-cured state. Adhesion can be exhibited.
- the resin layer 14 contains the second semi-cured resin, but may be made of the second semi-cured resin.
- the lower limit of the thickness of the resin layer 14 may be, for example, 2 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more.
- the upper limit of the thickness of the resin layer 14 may be, for example, 50 ⁇ m or less, 48 ⁇ m or less, 46 ⁇ m or less, or 45 ⁇ m or less.
- the thickness of the resin layer 14 may be adjusted within the ranges described above, and may be, for example, 2-50 ⁇ m, 10-50 ⁇ m, or 15-50 ⁇ m.
- the thickness of each resin layer 14 may be within the above range.
- the thickness of the plurality of resin layers 14 may be different, but it is preferable that all of the plurality of resin layers 14 have the same thickness.
- the peel adhesion strength of the resin layer 14 is measured based on the peel adhesion strength test specified in JIS K 6854: 1999 when adhered to a copper plate. For example, it may be a layer of more than 5 N/cm.
- the peel adhesive strength of the resin layer 14 when peeled at 90 degrees may be, for example, 6 N/cm or more, 8 N/cm or more, or 10 N/cm or more.
- the upper limit of the peel adhesive strength of the resin layer 14 when peeled at 90 degrees is not particularly limited, but may be, for example, 30 N/cm or less, 25 N/cm or less, or 20 N/cm or less.
- the upper limit of the curing rate of the second semi-cured resin is, for example, 50% or less, 48% or less, 46% or less, 42% or less, 40% or less, 38% or less, 36% or less, or 34% or less. good.
- the upper limit of the curing rate of the second semi-cured resin is within the above range, the second semi-cured resin melts moderately when the composite sheet 10 is heat-bonded to the adherend and fills the gaps on the surface of the adherend. Better adhesiveness can be exhibited by being filled.
- the lower limit of the curing rate of the second semi-cured resin may be, for example, 20% or more, 23% or more, or 25% or more.
- the flow of the second semi-cured resin from the resin layer is suppressed when the composite sheet 10 is heat-bonded to the adherend.
- a decrease in adhesion to the body can be more sufficiently suppressed.
- the curing rate of the second semi-cured resin may be adjusted within the above range, and may be, for example, 20-50%.
- a /B has a value of 0.5 to 1.7.
- the first semi-cured resin and the second semi-cured resin are semi-cured products of the same resin composition or similar resin compositions
- the value of A/B is 1.0
- the first semi-cured resin and the second semi-cured resin It means that the curing rates of the two semi-cured resins are almost the same.
- the value of A/B may be 0.5 or more and less than 1.0, 1.0, or more than 1.0 and 1.7 or less.
- the value of A/B is 0.5 or more and less than 1.0, the outflow of the semi-cured resin is suppressed when the composite sheet 10 and the adherend are bonded, and the resulting laminate has insulating properties. Decrease can be suppressed more.
- the value of A/B is more than 1.0 and 1.7 or less, the followability of the composite sheet 10 to the surface shape of the adherend when the composite sheet 10 and the adherend are adhered is further improved. can be improved.
- the lower limit of the value of A/B may be, for example, 0.6 or more, 0.8 or more, or 0.9 or more.
- the upper limit of the value of A/B may be, for example, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.0 or less.
- the value measured under the following conditions shall be used. Specifically, first, the composite sheet to be measured is heated at 100° C. to melt the resin layer containing the second semi-cured resin, which is then removed from the composite sheet by a squeegee to obtain a resin-filled plate. 2 mg of the removed second semi-cured resin is sampled and the calorific value is measured with a differential scanning calorimeter. The calorific value per unit mass of the obtained calorific value is calculated and defined as the calorific value B. Next, 10 mg of the resin-filled plate obtained as described above is sampled, and the calorific value is measured with a differential scanning calorimeter.
- the content of the first semi-cured resin is determined by cross-sectional SEM image analysis and thermogravimetric differential thermal analysis (TG-DTA) of the resin-filled plate to be measured, and the content of the determined first semi-cured resin and the above-mentioned
- the calorific value A of the first semi-cured resin is calculated from the calorific value of the resin-filled plate obtained by the measurement. From the calorific value A and the calorific value B thus obtained, the value of A/B can be determined.
- the differential scanning calorimetry is carried out by raising the temperature from room temperature to 330° C. at a rate of 10° C./min, and the exothermic peak generated in the process is measured.
- the second semi-cured resin those exemplified as the first semi-cured resin can be applied.
- the second semi-cured resin may be the same as or different from the first semi-cured resin.
- the composite sheet 10 described above can be manufactured, for example, by the following manufacturing method.
- An example of a method for producing a composite sheet includes an impregnation step of impregnating a porous nitride sintered plate with a first resin composition to obtain a resin-impregnated body, and heating the resin-impregnated body to form pores a curing step to obtain a resin-filled board containing a first semi-cured resin by semi-curing the resin composition filled in the resin-filled board; and a covering step provided on the part.
- a porous nitride sintered plate is impregnated with the first resin composition to obtain a resin-impregnated body having a resin composition layer on the main surface.
- An impregnation step and a resin-filled plate containing a first semi-cured resin are obtained by heating the resin-impregnated body to semi-cure the resin composition filled in the pores and the resin composition constituting the resin composition layer. and a curing step.
- 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 10.0 ⁇ m, or an average particle size of 3.0 to A 40.0 ⁇ m hexagonal boron nitride powder 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 by uniaxial pressing or cold isostatic pressing (CIP).
- a sintering aid may be incorporated to obtain 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 0.10 parts by mass with respect to a total of 100 parts by mass of the nitride and the sintering aid. It may be at least parts by mass.
- the amount of the sintering aid compounded is, for example, 20.00 parts by mass or less, 15.00 parts by mass or less, or 10.00 parts by mass or less with respect to a total of 100 parts by mass of the nitride and the sintering aid. good.
- 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 molded product may be a sheet-like shape with a thickness of 5.0 mm or less. If a nitride sintered plate is produced using such a sheet-like compact, a sheet-like composite sheet having a thickness of 8.0 mm or less can be produced without cutting the nitride sintered plate. can.
- 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 5.0 mm or less.
- 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, for example, 5.0 mm or less can be obtained by such a cutting process.
- the pores of the nitride sintered body are impregnated with the first resin composition having a viscosity of 10 to 500 mPa ⁇ s to obtain a resin-impregnated body.
- the impregnation of the first resin composition can be facilitated.
- the filling rate of the resin filler can be sufficiently increased.
- the viscosity of the first resin composition when the nitride sintered plate is impregnated with the first resin composition may be, for example, 440 mPa ⁇ s or less, 390 mPa ⁇ s or less, or 340 mPa ⁇ s or less. By reducing the viscosity of the first resin composition in this manner, the impregnation of the first resin composition can be sufficiently promoted.
- the viscosity of the first resin composition when the nitride sintered plate is impregnated with the first resin composition may be, for example, 15 mPa ⁇ s or more, or 20 mPa ⁇ s or more.
- the viscosity of the first resin composition may be adjusted within the range described above, and may be, for example, 15 to 440 mPa ⁇ s, or 20 to 340 mPa ⁇ s.
- the viscosity of the first resin composition may be adjusted by partially polymerizing the monomer component, or may be adjusted by adding a solvent.
- the above viscosity of the first resin composition is the viscosity at the temperature (T1) of the first resin composition when impregnating the nitride sintered plate with the first 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 when the nitride sintered plate is impregnated with the first resin composition may be adjusted.
- the temperature (T2) may be, for example, 80-140°C.
- Impregnation of the nitride sintered plate with the first 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 first resin composition, or the surface of the nitride sintered plate may be coated with the first resin composition. good.
- 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 filling rate of the resin in the resin filler may be adjusted.
- the median pore diameter of the nitride sintered plate is, for example, 0.3 to 6.0 ⁇ m, 0.5 to 5.0 ⁇ m, 1.0 to 4.0 ⁇ m, or 1.0 to 3.0 ⁇ m. It may be 5 ⁇ m.
- the first resin composition for example, one that becomes a semi-cured resin mentioned in the above description of the composite sheet by a semi-curing reaction can be used.
- the first 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-propano
- the first resin composition may be thermosetting, 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 an agent.
- 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 is within the above range, it is easy to prepare the resin-impregnated body.
- the content of the imidazole-based curing agent may be adjusted within the range described above. 001 to 0.1 parts by mass.
- the first resin composition may contain components other than the main agent and the curing agent.
- Other components further 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 first resin composition.
- the resin-filled plate containing the first semi-cured resin is prepared by semi-curing the first resin composition in the resin-impregnated body obtained in the impregnation step.
- the first resin composition is semi-cured by heating and/or light irradiation depending on the type of the first resin composition (or curing agent added as necessary).
- the heating temperature for semi-curing the first resin composition by heating may be, for example, 80 to 130°C.
- the first semi-cured resin obtained by semi-curing the first resin composition contains, as a resin component, at least one thermosetting resin selected from the group consisting of cyanate resins, bismaleimide resins, and epoxy resins. you can
- the first semi-cured resin may also contain a curing agent.
- the first semi-cured resin includes 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 curing step is preferably performed in a situation where the first resin composition exists around the resin-impregnated body.
- the first resin composition is supplied from the periphery of the resin-impregnated body, and the formation of voids can be further suppressed.
- the presence of the similar resin in the surroundings can also suppress the formation of voids.
- a composite sheet is prepared by providing a resin layer containing a second semi-cured resin on at least a portion of the main surface of the resin-filled plate.
- the coating step is, for example, a step of attaching the second resin composition to the resin-filled plate obtained in the curing step and heating the resin-filled plate to form a resin layer on at least part of the main surface of the resin-filled plate.
- the step may include providing a resin layer on at least part of the main surface of the resin-filled plate by bonding a semi-cured material of the second resin composition prepared in advance.
- the coating method in the coating step is not particularly limited, and the resin-filled plate may be immersed in the second resin composition, or the surface of the resin-filled plate may be coated with the second resin composition. Alternatively, a separately prepared resin layer containing a second semi-cured resin may be adhered. Means for adhering a separately prepared resin layer may be a method of transferring a resin layer separately provided on a support. The amount of the second resin composition adhering to the resin filler may be adjusted by the viscosity of the second resin composition.
- the viscosity of the second resin composition when adhered to the resin-filled plate may be, for example, 10 to 500 mPa ⁇ s, or 15 to 400 mPa ⁇ s.
- the viscosity of the second resin composition is the viscosity at the temperature (T4) of the second resin composition when the second resin composition adheres to the resin filling.
- the viscosity is measured using a rotational viscometer at a shear rate of 10 (1/sec) and under temperature (T4).
- T4 the viscosity at which the second resin composition adheres to the resin filling may be adjusted.
- This viscosity may be adjusted by changing the temperature (T4) of the second resin composition, or may be adjusted by changing the blending amount of the solvent as in the case of the first resin composition.
- the components contained in the second resin composition may be the same as those exemplified for the first resin composition.
- the compositions of the second resin composition and the first resin composition may be the same or different.
- the second resin composition is semi-cured to obtain the second resin.
- the second resin composition is semi-cured by heating and/or light irradiation depending on the type of the second resin composition (or curing agent added as necessary).
- the heating temperature for semi-curing the second resin composition by heating may be, for example, 80 to 130°C.
- the first The hardening rate of the second resin can also be lower than the hardening rate of the resin.
- the second semi-cured resin obtained by semi-curing the second resin composition includes, as resin components, at least one thermosetting resin selected from the group consisting of cyanate resins, bismaleimide resins and epoxy resins, and a curing agent. may contain In addition to these components, the second semi-cured resin includes 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 manufacturing method described above may have other steps such as a sintering step, an impregnation step, a curing step, and a coating step.
- Other steps include, for example, a step of removing impurities from the surface of the nitride sintered body or the surface of the composite sheet obtained through the coating step.
- Production method B adjusts the amount of the first resin composition to be impregnated into the nitride sintered plate in the impregnation step in production method A so that a resin composition layer is formed on the resin impregnated body, thereby coating It is a method for preparing a composite sheet without providing a separate step.
- the thickness of the resin composition layer can be adjusted using, for example, a scraper and an applicator. For other conditions, the contents described in the description of the manufacturing method A can be applied.
- the laminate includes an insulating sheet and a metal sheet provided on at least one main surface of the insulating sheet, and the insulating sheet is a cured product of the composite sheet described above. That is, in one aspect of the laminate, the cured resin-filled plate, the cured resin layer, and the metal sheet are provided in this order. In this case, the cured resin-filled body and the metal sheet are joined via the cured resin layer.
- 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 sheet 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.
- the lower limit of the surface roughness Rz of the main surface of the metal sheet on the insulating sheet side may be, for example, 20 ⁇ m or more, 25 ⁇ m or more, or 30 ⁇ m or more. Since the laminate is obtained by laminating the above-mentioned composite sheet with a metal sheet and then curing the laminate, even if the surface roughness of the metal sheet is large, the laminate can be sufficiently strongly bonded.
- the upper limit of the surface roughness Rz of the main surface of the metal sheet on the insulating sheet side may be, for example, 50 ⁇ m or less, 45 ⁇ m or less, or 40 ⁇ m or less.
- the surface roughness Rz of the main surface of the metal sheet on the insulating sheet side may be adjusted within the range described above, and may be, for example, 20 to 50 ⁇ m, or 20 to 40 ⁇ m. Note that the composite sheet 10 according to the present disclosure can exhibit sufficient adhesiveness even if the surface roughness Rz of the main surface of the metal sheet on the insulating sheet side is small. From this point of view, the surface roughness Rz of the main surface of the metal sheet on the insulating sheet side may be, for example, 1 to 15 ⁇ m, 2 to 10 ⁇ m, or 3 to 10 ⁇ m.
- the surface roughness Rz in this specification is the maximum height roughness specified in JIS B 0601: 2013 "Use of product geometric properties (GPS) - surface texture: contour curve method - terms, definitions and surface texture parameters" means.
- the surface roughness Rz is a value measured according to JIS B 0601:2013.
- FIG. 3 is a cross-sectional view showing an example of a laminate.
- FIG. 3 shows a cross section of the laminate 20 cut along the lamination direction.
- the laminate 20 includes an insulating sheet 15 that is a cured product of the composite sheet 10 of FIGS. 1 and 2, and metal sheets 22 laminated on both main surfaces of the insulating sheet 15 .
- 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 main surfaces of the insulating sheet 15 . In a modification, only one main surface of the insulating sheet 15 may be provided with the metal sheet 22 .
- the metal sheet 22 in the laminate 20 is adhered to the resin-filled plate cured product 16 by the cured resin layer 18 with high adhesion. Thereby, the metal sheet 22 and the insulating sheet 15 are strongly bonded. Since the metal sheet 22 and the insulating sheet 15 are adhered to each other with high adhesiveness, the laminated body 20 can be suitably used as a heat dissipation member for 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 laminate 20 includes the insulating sheet 15 that is the cured product of the composite sheet 10, both thermal conductivity and insulation reliability can be achieved at high levels.
- One embodiment of a method for manufacturing a laminate has a lamination step of laminating the above-described composite and metal sheets, followed by heating and pressing.
- the composite a composite obtained by any of the above-described production methods 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. With the main surfaces of the composite 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 applied. It should be noted that the pressurization and heating do not necessarily have to be performed at the same time, and the heating may be performed after the 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 plate was taken out from the boron nitride container. Thus, a sheet-like boron nitride sintered plate was obtained. The thickness of the boron nitride sintered plate was 0.3 mm.
- the amount of the first resin composition dropped was 1.5 times the total volume of the pores of the boron nitride sintered plate.
- the amount of the first resin composition that was dropped A part remained on the main surface without impregnating the boron nitride sintered plate.
- the first resin composition remaining on the upper main surface of the boron nitride sintered plate was smoothed using a stainless steel scraper (manufactured by Narby Co., Ltd.). An excess of the first resin composition was removed to obtain a resin-impregnated body having a smooth main surface.
- the resin-impregnated body was heated at 120°C for 180 minutes under atmospheric pressure to semi-cure the first resin composition.
- the boron nitride sintered body was exposed on a part of the main surface of the resin-filled plate.
- a resin composition was prepared by the same method as that for preparing the resin-filled plate, and was used as a second resin composition.
- the second resin composition was heated at 120° C. for 300 minutes to obtain a second semi-cured resin.
- the second semi-cured resin was dripped onto one main surface of the resin-filled plate while maintaining its temperature. Under atmospheric pressure, the second semi-cured resin dropped onto the main surface of the resin-filled plate is spread using a silicone rubber spatula, spread over the entire main surface, and then cooled to room temperature to solidify and fill with resin.
- a resin layer was provided on one major surface of the plate. The thickness of the resin layer was 45 ⁇ m.
- the second resin composition is heated at 120° C.
- a second semi-cured resin Dropped onto the main surface. Under atmospheric pressure, the second semi-cured resin dropped onto the other main surface of the resin-filled plate is spread using a silicone rubber spatula, spread over the entire main surface, and then cooled to room temperature to solidify. A resin layer was provided on the other surface of the resin-filled plate. The thickness of the resin layer was also 45 ⁇ m. Thus, a composite sheet was obtained in which resin layers containing the second semi-cured resin were provided on both main surfaces of the resin-filled plate.
- the ratio (value of A/B) of the amount of heat generated during curing of the first semi-cured resin to the amount of heat generated during curing of the second semi-cured resin was measured according to the following procedure. First, the composite sheet was heated at 100° C. to melt the second semi-cured resin, which was then removed from the composite sheet by a squeegee to obtain a resin-filled plate. 2 mg of the removed second semi-cured resin was sampled and heated from room temperature to 330° C.
- the adhesion was evaluated according to the following criteria. Table 1 shows the results.
- Example 2-5 Using a boron nitride sintered plate whose porosity, median pore diameter and thickness are shown in Table 1, and that the curing rates of the first semi-cured resin and the second semi-cured resin are the values shown in Table 1.
- a composite sheet was prepared in the same manner as in Example 1, except that it was adjusted to be Table 1 shows the peel strength of the resin layer and the A/B value of the resulting composite sheet. Furthermore, the obtained composite sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.
- Table 1 shows the use of a boron nitride sintered plate having a porosity, median pore diameter, and thickness shown in Table 1, and the curing rates of the first semi-cured resin and the second semi-cured resin.
- a composite sheet was prepared in the same manner as in Example 1, except that the values were adjusted.
- Table 1 shows the peel strength of the resin layer and the A/B value of the resulting composite sheet. Furthermore, the obtained composite sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.
- the present disclosure it is possible to provide a composite sheet that can exhibit sufficient adhesiveness to an adherend even when the surface roughness of the adherend is relatively large.
- the present disclosure can also provide laminates prepared using the composite sheets described above.
- SYMBOLS 10 Composite sheet, 12... Resin-filled board, 12a... Main surface, 14... Resin layer, 20... Laminate, 22... Metal sheet, 15... Insulating sheet, 16... Hardened resin-filled plate, 18... Hardened resin layer.
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Abstract
L'invention concerne , selon un certain aspect, une feuille composite ayant une plaque remplie de résine comprenant une plaque frittée de nitrure poreux et une première résine semi-durcie remplissant des pores de la plaque frittée de nitrure et une couche de résine comprenant une seconde résine semi-durcie disposée sur au moins une partie d'une surface principale de la plaque remplie de résine, et la valeur d'A/B étant de 0,5 à 1,7, où A est la valeur calorifique accompagnant le durcissement de la première résine semi-durcie et B est la valeur calorifique accompagnant le durcissement de la seconde résine semi-durcie, mesurées par l'utilisation d'un calorimètre à balayage différentiel.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2016103611A (ja) * | 2014-11-28 | 2016-06-02 | デンカ株式会社 | 窒化ホウ素樹脂複合体回路基板 |
JP2019145744A (ja) * | 2018-02-23 | 2019-08-29 | イビデン株式会社 | 伝熱基板 |
WO2021230328A1 (fr) * | 2020-05-15 | 2021-11-18 | デンカ株式会社 | Composite, et stratifié |
WO2022209325A1 (fr) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | Composite, son procédé de fabrication, plaque remplie de résine, stratifié et son procédé de fabrication |
WO2022209971A1 (fr) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | Corps composite et son procédé de fabrication, et corps stratifié et son procédé de fabrication |
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JP7458479B2 (ja) | 2020-05-15 | 2024-03-29 | デンカ株式会社 | 複合体及び複合体の製造方法 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2016103611A (ja) * | 2014-11-28 | 2016-06-02 | デンカ株式会社 | 窒化ホウ素樹脂複合体回路基板 |
JP2019145744A (ja) * | 2018-02-23 | 2019-08-29 | イビデン株式会社 | 伝熱基板 |
WO2021230328A1 (fr) * | 2020-05-15 | 2021-11-18 | デンカ株式会社 | Composite, et stratifié |
WO2022209325A1 (fr) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | Composite, son procédé de fabrication, plaque remplie de résine, stratifié et son procédé de fabrication |
WO2022209971A1 (fr) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | Corps composite et son procédé de fabrication, et corps stratifié et son procédé de fabrication |
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