WO2023027123A1 - 複合シート、及び複合シートの製造方法、並びに、積層基板 - Google Patents

複合シート、及び複合シートの製造方法、並びに、積層基板 Download PDF

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Publication number
WO2023027123A1
WO2023027123A1 PCT/JP2022/031929 JP2022031929W WO2023027123A1 WO 2023027123 A1 WO2023027123 A1 WO 2023027123A1 JP 2022031929 W JP2022031929 W JP 2022031929W WO 2023027123 A1 WO2023027123 A1 WO 2023027123A1
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Prior art keywords
composite sheet
thermosetting resin
ceramic plate
resin composition
less
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PCT/JP2022/031929
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English (en)
French (fr)
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 JP2023514475A priority Critical patent/JP7263634B1/ja
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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/10—Arrangements for heating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/20—Arrangements for cooling
    • H10W40/25—Arrangements for cooling characterised by their materials

Definitions

  • the present disclosure relates to a composite sheet, a method for manufacturing the composite sheet, and a laminated substrate.
  • Components such as power devices, transistors, thyristors, and CPUs are required to efficiently dissipate the heat generated during use.
  • a composite sheet composed of a resin and a ceramic such as boron nitride is used as a heat dissipation member for such an insulating layer and thermal interface material.
  • a composite sheet in which a porous ceramic plate (for example, a boron nitride sintered plate) is impregnated with a resin is being studied (for example, see Patent Document 1).
  • a porous ceramic plate for example, a boron nitride sintered plate
  • a resin-impregnated boron nitride sintered body in which 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 ceramic circuit board obtained by connecting the above-described ceramic plate to the circuit board is required to have sufficiently high reliability depending on the application. For example, as in power devices, it is required to maintain excellent reliability even under severe heat cycle conditions. However, even composite sheets that do not show a significant difference in appearance may not exhibit the expected adhesiveness, making them unsuitable for use in fields requiring high reliability. There was room for improvement.
  • An object of the present disclosure is to provide a composite sheet with excellent adhesion and a method for manufacturing the same. Another object of the present disclosure is to provide a laminated substrate having excellent heat cycle characteristics.
  • thermosetting resin In the composite sheet as described above, the thermosetting resin is maintained in a semi-cured state, and when it is connected to an adherend such as a metal sheet, the thermosetting resin is further cured to improve adhesion to the adherend. We are trying to improve. As a result of detailed investigation by the present inventors regarding the above-mentioned problem, there are cases where the composite sheet before being connected to the adherend is dotted with portions where the curing of the thermosetting resin is accelerated. It is one of the causes of the deterioration of adhesion to the adherend, and the acceleration of curing of the thermosetting resin in the composite sheet is due to impurities adhered to the ceramic plate used when manufacturing the composite sheet.
  • thermosetting resin even if the portion where the curing of the thermosetting resin is accelerated as described above does not have any particular difference in appearance, it may affect the adhesion to the adherend, and such
  • light is applied from one main surface of the composite sheet, and the hardening of the thermosetting resin progresses by observing from the other main surface side. It was found that the dark part can be easily detected as a dark color area. The present disclosure is made based on the above findings.
  • One aspect of the present disclosure is a cleaning step including maintaining a ceramic plate having pores in a reduced pressure environment for a predetermined time and contacting it with a solvent containing water, and applying a thermosetting resin composition to the ceramic plate
  • a cleaning step including maintaining a ceramic plate having pores in a reduced pressure environment for a predetermined time and contacting it with a solvent containing water, and applying a thermosetting resin composition to the ceramic plate
  • a method for producing a composite sheet comprising an impregnation step of impregnating an object, and a semi-curing step of heating and semi-curing the thermosetting resin composition filled in the pores.
  • the manufacturing method of the composite sheet facilitates the impregnation of the thermosetting resin by including a washing step for reducing impurities adhering to the ceramic plate, and the degree of hardening of the thermosetting resin in the composite sheet is controlled. Variation can be suppressed. Therefore, the resulting composite sheet can exhibit excellent adhesiveness.
  • One aspect of the present disclosure is a composite sheet comprising a ceramic plate having pores and a thermosetting resin filled in the pores, and irradiating light from one main surface side of the composite sheet In this state, an observation image is obtained from the other main surface side, and when the dark color region is specified by binarizing the observation image, the ratio of the area of the dark color region is 0.5%.
  • a composite sheet is provided that is less than
  • the area ratio of the dark-colored region corresponding to the portion where the curing of the thermosetting resin is accelerated is kept low, and the degree of curing of the thermosetting resin within the composite sheet is uniform. suppressed. This allows the composite sheet to exhibit excellent adhesiveness.
  • the difference between the hardening rate of the thermosetting resin in the dark-colored area and the hardening rate of the thermosetting resin in the area other than the dark-colored area may be less than 5%.
  • One aspect of the present disclosure provides a laminated substrate comprising the composite sheet described above and a metal layer provided on the composite sheet.
  • the laminated substrate includes the composite sheet described above, it can exhibit excellent adhesiveness between the composite sheet and the metal layer.
  • FIG. 1 is a perspective view showing an example of a composite sheet.
  • FIG. 2 is a cross-sectional view showing an example of a laminated substrate.
  • 3 is a grayscale image of the surface images of the composite sheets of Example 1 and Comparative Example 1.
  • FIG. 4 is a binarized image of the grayscaled image of FIG.
  • 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. .
  • the numerical range indicated by “ ⁇ to ⁇ ” means “ ⁇ or more and ⁇ or less” unless otherwise specified.
  • One embodiment of a method for producing a composite sheet includes a washing step including maintaining a ceramic plate having pores in a reduced pressure environment for a predetermined time and contacting it with a solvent containing water, and applying heat to the ceramic plate. It has an impregnation step of impregnating the curable resin composition, and a semi-curing step of heating and semi-curing the thermosetting resin composition filled in the pores.
  • a commercially available ceramic plate may be used as the ceramic plate, or a separately prepared one may be used. That is, the method for producing a ceramic plate further includes, for example, forming a raw material powder containing a nitride and a sintering aid to prepare a compact, and firing the compact to obtain a ceramic plate. good too.
  • the molded body may be block-shaped or plate-shaped.
  • a ceramic plate may be obtained by processing the block-shaped ceramic obtained by firing into a plate.
  • the nitride contained in the raw material powder may be at least one nitride selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride.
  • the nitride may further include, for example, boron carbonitride.
  • the ceramic plate or ceramic may be a sintered nitride, preferably a sintered body containing boron nitride, more preferably a sintered boron nitride body.
  • 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 a hexagonal crystal having an average particle size of 3.0 to 40 ⁇ m. Boron nitride powder can be used.
  • sintering aids contained in the raw material powder 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 blending amount of the sintering aid is, for example, 0.01 parts by mass or more, 0.10 parts by mass or more, 0.50 parts by mass or more, and 1.0 parts by mass or more, with respect to a total of 100 parts by mass of the nitride and the sintering aid. 00 parts by mass or more, or 5.00 parts by mass or more.
  • 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. you can By setting the blending amount of the sintering aid within the above range, it becomes easier to adjust the median pore diameter of the ceramic plate within the range described below.
  • the amount of the sintering aid may be adjusted within the above range, for example, 0.01 to 20.00 parts by mass, or 5.00 parts by mass with respect to a total of 100 parts by mass of the nitride and the sintering aid. It may be up to 20.00 parts by mass.
  • the molded body can be prepared by molding the raw material powder.
  • the molding may be carried out by uniaxial pressing, cold isostatic pressing (CIP), or doctor blade.
  • 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.
  • its thickness may be, for example, less than 2.0 mm. Material loss due to processing can be reduced by forming the block-shaped ceramics into a sheet form from the stage before firing, as compared with the case where block-shaped ceramics are cut into plates after preparation. Therefore, the ceramic plate can be manufactured with a high yield.
  • the firing temperature of the compact may be, for example, 1600°C or higher, 1650°C or higher, 1700°C or higher, or 1800°C or higher.
  • the firing temperature of the compact may be, for example, 2200° C. or lower, 2100° C. or lower, or 2000° C. or lower.
  • the firing temperature may be adjusted within the ranges mentioned above, and may be, for example, 1600-2200°C, 1700-2100°C, or 1800-2100°C.
  • the firing time may be, for example, 1 hour or longer, 2 hours or longer, 3 hours or longer, or 5 hours or longer, and may be 30 hours or shorter, or 20 hours or shorter.
  • the firing time may be adjusted within the ranges mentioned above, and may be, for example, 2-20 hours, 3-15 hours, or 4-10 hours.
  • the atmosphere during firing may be, for example, an inert gas atmosphere such as nitrogen, helium, and argon.
  • a batch type furnace or 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 ceramic or ceramic plate can be obtained.
  • the ceramics obtained after the firing described above may be block-shaped. If the ceramic is block-shaped, a cutting step may be performed to process the ceramic to a thickness of less than 2 mm. In the cutting step, the ceramic is cut using, for example, a wire saw.
  • the wire saw may be, for example, a multi-cut wire saw or the like.
  • a ceramic plate having a thickness of less than 2 mm, for example, can be obtained by such a cutting process.
  • the amount of impurities present on the surface of the ceramic plate is removed by subjecting the ceramic plate to a treatment including maintaining the ceramic plate in a reduced pressure environment for a predetermined time and contacting the ceramic plate with a solvent containing water.
  • Reduce. Impurities may include subcomponents contained in the ingredients of the raw material powder, subcomponents generated during the firing process, and the like.
  • the order of the processes of maintaining the ceramic plate under a reduced pressure environment for a predetermined time and contacting the ceramic plate with a solvent containing water is not particularly limited, and can be repeated multiple times.
  • the washing step may be, for example, a step of keeping the ceramic plate in a reduced pressure environment for a predetermined time and then contacting the ceramic plate with a solvent containing water.
  • a reduced-pressure environment when the ceramic plate is maintained in a reduced-pressure environment for a predetermined time means that the pressure in the space where the ceramic plate is placed is, for example, less than 10000 Pa, and can also be called a vacuum environment.
  • the upper limit of the pressure in the reduced pressure environment may be, for example, 8000 Pa or less, 6500 Pa or less, 6000 Pa or less, 5000 Pa or less, 4000 Pa or less, or 3000 Pa or less.
  • the upper limit of the pressure is within the above range, it is possible to further reduce the components attached to the ceramic plate, and further accelerate the partial curing of the resin in the subsequent semi-curing step of the thermosetting resin. can be suppressed.
  • the lower limit of the pressure in the reduced-pressure environment is not particularly limited, but may be, for example, 100 Pa or higher, or 1000 Pa or higher. By setting the lower limit of the pressure within the above range, an increase in manufacturing cost of the composite sheet can be suppressed.
  • the pressure in the reduced pressure environment may be adjusted within the ranges described above, eg, 100-8000 Pa, 1000-6000 Pa, 1000-4000 Pa, or 1000-3000 Pa.
  • the lower limit of the time for which the ceramic plate is maintained under the reduced pressure environment for a predetermined time may be, for example, 5 minutes or more, 10 minutes or more, or 15 minutes or more. When the lower limit of the time during which the ceramic plate is maintained under the reduced pressure environment for the predetermined time is within the above range, the volatile components on the surface of the ceramic plate can be removed more sufficiently.
  • the upper limit of the time for which the ceramic plate is maintained under the reduced pressure environment for a predetermined time may be, for example, 60 minutes or less, 45 minutes or less, 40 minutes or less, or 30 minutes or less. When the upper limit of the time for which the ceramic plate is maintained under the reduced pressure environment for a predetermined time is within the above range, the manufacturing time of the composite sheet can be shortened.
  • the time for which the ceramic plate is maintained under the reduced pressure environment for a predetermined period of time may be adjusted within the range described above, and may be, for example, 5 to 60 minutes or 15 to 45 minutes.
  • the method of bringing the ceramic plate into contact with the water-containing solvent may be, for example, a method of spraying the water-containing solvent onto the ceramic plate, or a method of immersing the ceramic plate in the water-containing solvent.
  • the solvent containing water may contain an organic solvent in addition to water, or may consist of water only.
  • organic solvents include alcohol and acetone.
  • the alcohol a lower alcohol is preferable because it is easy to remove later, and for example, methanol and ethanol may be used.
  • the content of the organic solvent may be, for example, less than 50% by volume, or less than 30% by volume, based on the total amount of the solvent, 5% by volume or more, or 10% by volume. or more.
  • the lower limit of the time for which the ceramic plate is brought into contact with the solvent containing water may be, for example, 5 minutes or longer, 10 minutes or longer, or 15 minutes or longer. When the lower limit of the time for which the ceramic plate is brought into contact with the water-containing solvent is within the above range, solvent-soluble components on the surface of the ceramic plate can be removed more sufficiently.
  • the upper limit of the time for which the ceramic plate is brought into contact with the water-containing solvent may be, for example, 60 minutes or less, 45 minutes or less, or 30 minutes or less. Excessive water absorption of the ceramic plate can be suppressed by setting the upper limit of the time during which the ceramic plate is brought into contact with the water-containing solvent to be within the above range.
  • the time for which the ceramic plate is brought into contact with the solvent containing water may be adjusted within the range described above, and may be, for example, 5 to 60 minutes.
  • the solvent may remain on the surface of the ceramic plate. It is preferable to reduce the residual amount of
  • the ceramic plate is impregnated with the thermosetting resin composition to prepare a resin-impregnated body.
  • An impregnation device or the like can also be used to impregnate the ceramic plate with the thermosetting resin composition.
  • the upper limit of the viscosity of the thermosetting resin composition when the ceramic plate is impregnated with the thermosetting resin composition may be, for example, 440 mPa ⁇ s or less, 390 mPa ⁇ s or less, or 340 mPa ⁇ s or less.
  • the lower limit of the viscosity of the thermosetting resin composition when the ceramic plate is impregnated with the thermosetting resin composition may be, for example, 15 mPa ⁇ s or more, or 20 mPa ⁇ s or more.
  • thermosetting resin composition By setting a lower limit for the viscosity of the thermosetting resin composition, it is possible to further suppress the flow of the thermosetting resin composition once impregnated into the pores from the pores.
  • the viscosity of the thermosetting resin composition may be adjusted by partially polymerizing the monomer component, or may be adjusted by adding a solvent.
  • the above viscosity of the thermosetting resin composition is the viscosity at the temperature (T1) of the thermosetting resin composition when impregnating the ceramic plate with the thermosetting 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 ceramic plate is impregnated with the thermosetting resin composition may be adjusted.
  • the temperature (T2) may be, for example, 80-140°C.
  • Impregnation of the thermosetting resin composition into the ceramic plate may be performed under pressure or under reduced pressure.
  • the impregnation method is not particularly limited, and the ceramic plate may be immersed in the thermosetting resin composition, or the surface of the ceramic plate may be coated with the thermosetting resin composition.
  • the impregnation step may be carried out under atmospheric pressure or under either reduced pressure or increased pressure, and impregnation under reduced pressure and impregnation under increased pressure may be combined. good too.
  • 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 40 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, 6 MPa or higher, 10 MPa or higher, or 30 MPa or higher.
  • the median pore diameter of the pores in the ceramic plate is, for example, 0.3 to 6.0 ⁇ m, 0.5 to 5.0 ⁇ m, 1.0 to 4.0 ⁇ m, or 2.0 to 4.0 ⁇ m.
  • thermosetting resin composition contains, 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. good.
  • 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, for example, 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 It may be 3 parts by mass or less.
  • 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 at least parts by mass.
  • the content of the phosphine-based curing agent is within the above range, it is easy to prepare the resin-impregnated body.
  • 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 weight, or 0.5 to 3 parts by weight.
  • 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 at least parts by mass.
  • the content of the imidazole-based curing agent may be adjusted within the range described above. 001 to 0.1 parts by weight, or 0.005 to 0.03 parts by weight.
  • the thermosetting resin composition may contain components other than the main agent and 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 thermosetting resin composition.
  • the thermosetting resin composition may be used together with a solvent.
  • solvents include aliphatic alcohols such as ethanol and isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol, 2-(2-methoxyethoxy ) ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol and other ether alcohols, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and other glycol ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl Ketones such as ketones, and hydrocarbons such as toluene and xylene.
  • solvents include aliphatic alcohols such as ethanol and isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol
  • thermosetting resin composition filled in the pores is heated and semi-cured.
  • the ceramic plate impregnated with the thermosetting resin composition is heat-treated to semi-harden the thermosetting resin composition to obtain a semi-hardened product containing the thermosetting resin.
  • the cured state of the thermosetting resin composition in the composite sheet can be adjusted, and a semi-cured state can be obtained.
  • the heating temperature in the semi-curing step can be adjusted according to the components and composition of the thermosetting resin composition, and may be, for example, 80 to 130°C.
  • the heating time in the semi-curing step may be, for example, 1 to 10 hours, or 1 to 5 hours.
  • the heat treatment in the semi-curing step may be performed under atmospheric pressure or under pressure.
  • the semi-cured (also referred to as B-stage) state means that it is in a state where it can be further cured by a subsequent curing treatment.
  • the semi-cured state can also be utilized to temporarily press-bond to an adherend such as a metal layer, and then heat to adhere to the adherend.
  • the semi-cured material is in a semi-cured state, and can be brought into a completely cured (also referred to as C-stage) state by further curing treatment. Whether or not the semi-cured material in the composite sheet is in a semi-cured state capable of further curing can be confirmed by, for example, a differential scanning calorimeter.
  • thermosetting resin composition impregnated in the pores of the ceramic plate
  • the semi-cured product of the thermosetting resin composition includes a thermosetting resin obtained by reacting the raw material components (compounds contained in the thermosetting resin composition, etc.) in the thermosetting resin composition. It's okay.
  • the semi-cured product may contain, in addition to the thermosetting resin, unreacted compounds among the raw material components.
  • the curing rate of the thermosetting resin composition may be used as an index, with the curing rate being 100% when the fully cured state is reached.
  • the curing rate of the semi-cured material may be, for example, 70% or less, 65% or less, or 60% or less.
  • the adhesiveness of the composite sheet to the adherend can be improved.
  • the curing rate of the semi-cured product may be, for example, 5% or more, 10% or more, 15% or more, 20% or more, 30% or more, or 40% or more.
  • the curing rate of the semi-cured material When the curing rate of the semi-cured material is within the above range, the semi-cured material can be suppressed from flowing out of the composite sheet, the semi-cured material can be sufficiently retained in the pores of the ceramic plate, and the insulating property can be improved. can be raised enough.
  • the curing rate of the semi-cured product may be adjusted within the range described above, and may be, for example, 5-70%, 15-65%, or 30-60%.
  • the curing rate can be determined by measurement using a differential scanning calorimeter.
  • the curing rate of the semi-cured product can be determined by measurement using a differential scanning calorimeter.
  • the calorific value Q per unit mass generated when 2 mg of the uncured resin composition is completely cured is measured.
  • 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.
  • the mass of the sample used for the measurement with the differential scanning calorimeter is the same as that of the thermosetting resin composition used for the measurement of the calorific value Q.
  • the composite sheet obtained by heat treatment has a semi-cured thermosetting resin composition.
  • the semi-cured product may contain at least one thermosetting resin selected from the group consisting of cyanate resins, bismaleimide resins and epoxy resins, and a curing agent.
  • the semi-cured product may contain other resins such as phenolic resins, melamine resins, urea resins, and alkyd resins, as well as silane coupling agents, leveling agents, and antifoaming agents. It may contain ingredients derived from agents, surface conditioners, wetting and dispersing agents, and the like.
  • the total content of the other resin and the component 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 semi-cured product.
  • Thermosetting resins include, for example, epoxy resins, silicone resins, cyanate resins, silicone rubbers, acrylic resins, phenolic resins, melamine resins, urea resins, bismaleimide resins, unsaturated polyesters, fluorine resins, polyimides, polyamideimides, polyethers.
  • polysulfone liquid crystal polymer
  • polyethersulfone polycarbonate
  • maleimide resin maleimide-modified resin
  • ABS acrylonitrile-butadiene-styrene
  • AAS At least one selected from the group consisting of acrylonitrile-acrylic rubber-styrene) resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin, polyglycolic acid resin, polyphthalamide, and polyacetal may be included.
  • One embodiment of the composite sheet comprises a ceramic plate having pores and a thermosetting resin filling the pores.
  • FIG. 1 is a perspective view showing an example of the composite sheet 10.
  • the composite sheet 10 includes a porous ceramic plate 20 having a thickness t of less than 2 mm and a thermosetting resin filling the pores of the ceramic plate 20 .
  • the ceramic plate 20 may be, for example, a nitride sintered plate.
  • the nitride sintered plate contains nitride particles and pores formed by sintering nitride primary particles.
  • the nitride sintered plate may be a boron nitride sintered plate.
  • the composite sheet 10 is irradiated with light from one main surface side (for example, the main surface 10b side in FIG. 1) of the composite sheet, and then from the other main surface side (for example, the main surface 10a side in FIG. 1). is obtained, and the area ratio of the dark color region is less than 0.5% when the dark color region is specified by binarizing the observation image. Dark areas correspond well to areas where the curing of the thermosetting resin has progressed more than other locations.
  • the upper limit of the area ratio of the dark color region is less than 0.5%, but may be, for example, 0.3% or less, 0.2% or less, or 0.1% or less, and 0% (dark color region is not observed).
  • the upper limit of the ratio of the area of the dark-colored region is within the above range, the adhesiveness to the adherend is more excellent.
  • the lower limit of the ratio of the area of the dark color region is not particularly limited, it may be, for example, 0.01% or more, or 0.05% or more.
  • the area ratio of the dark color region may be adjusted within the above range, and may be, for example, 0.01 to 0.3%, 0.01 to 0.2%.
  • the observation of the above dark-colored areas shall be performed by the following method.
  • a measurement sample is placed on a thin LED trace table, and a black cylinder is placed around the measurement sample to reduce the influence of the surroundings.
  • An image is then acquired from the top surface of the measurement sample with the brightness of the thin LED trace stage set to maximum intensity.
  • the acquired image is imported into image analysis software, converted to grayscale, the brightness threshold is checked in 255 steps, and the threshold value is 230 from black to white, and binarization is performed. Adjust the image.
  • the black area is defined as a dark color area, and the area ratio of the dark color area is determined by the above image analysis software.
  • thermosetting resin changes color when cured, the same phenomenon occurs regardless of the type of thermosetting resin, and the same evaluation is possible.
  • the threshold value may be determined based on the determination method described above, and the specific threshold value may be changed depending on the type of resin. For example, if a grayscale pattern is observed in the image after conversion to gray scale (for example, (b) in FIG. 3), binarize it to obtain an image in which the grayscale pattern corresponds to black and white (for example, FIG. 4 (b)), the binarization threshold can be set.
  • the difference between the hardening rate of the thermosetting resin in the dark-colored area and the hardening rate of the thermosetting resin in the area other than the dark-colored area is small.
  • the difference in cure rate may be, for example, less than 5%, 4% or less, 3% or less, or 2% or less. Adhesiveness can be further improved by setting the difference in curing rate within the above range.
  • the upper limit of the thickness of the composite sheet 10 may be, for example, 2.2 mm or less, 2.0 mm or less, 1.8 mm or less, 1.5 mm or less, 1.3 mm or less, or 1.0 mm or less.
  • the lower limit of the thickness of the composite sheet 10 may be, for example, 0.1 mm or more, or 0.2 mm or more.
  • the laminated substrate obtained using the composite sheet 10 can have more excellent heat cycle characteristics.
  • the thickness of the composite sheet 10 may be adjusted within the ranges described above, and may be, for example, 0.1-2.2 mm, 0.1-1.5 mm, or 0.2-1.0 mm.
  • the thickness of the composite sheet 10 means a value measured along the direction perpendicular to the main surfaces 10a, 10b. When the thickness of the composite sheet 10 is not constant, the thickness is measured at 10 arbitrary points, and the arithmetic average value is taken as the thickness of the composite sheet 10 .
  • the filling rate of the thermosetting resin may be adjusted from the viewpoint of further increasing the adhesiveness of the composite sheet, and may be, for example, 90 to 100% by volume or 94 to 100% by volume.
  • the filling rate of the thermosetting resin in this specification means the value obtained by the following formula (B).
  • the ceramic plate is a boron nitride sintered plate
  • 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 is a value obtained by the following formula (C).
  • Theoretical density of composite sheet bulk density of boron nitride sintered plate + true density of resin x (1 - bulk density of boron nitride sintered plate / true density of boron nitride) ... (C)
  • 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". (Refer to formulas (14) to (17) in item 11 of JIS Z 8807:2012).
  • the composite sheet described above has excellent adhesion to adherends such as metal layers, and is therefore useful as an adhesive member for applications that require thermal conductivity and insulation.
  • the composite sheet described above can be used as an adhesive member for bonding metal circuits and other layers in power module structures, LED light emitting devices, and the like. That is, the composite sheet described above is suitable for manufacturing laminated substrates.
  • FIG. 2 is a cross-sectional view of an example of a laminated substrate cut in the thickness direction.
  • the laminated substrate 100 includes a composite sheet 10 , a metal layer 30 adhered to the principal surface 10 a of the composite sheet 10 , and a metal layer 40 adhered to the principal surface 10 b of the composite sheet 10 .
  • the metal layers 30 and 40 may be, for example, metal plates or metal foils.
  • the metal layers 30 and 40 may also have patterns such as circuits, for example.
  • Materials for the metal layers 30 and 40 include, for example, aluminum and copper.
  • the material, thickness, presence/absence of patterns, etc. of the metal layers 30 and 40 may be the same or different.
  • the thickness of the metal layers 30, 40 may be, independently of each other, for example 0.035 mm or more or 10 mm or less.
  • the laminated substrate 100 may have a resin layer between the composite sheet 10 and the metal layers 30 and 40 within the scope of the present disclosure. This resin layer may be formed by curing the resin exuded from the composite sheet 10 .
  • the composite sheet 10 and the metal layers 30 and 40 in the laminated substrate 100 are sufficiently firmly adhered by the exuded resin, and thus have excellent adhesiveness. Since such a laminated substrate is thin and has excellent adhesion and heat dissipation properties, it can be suitably used as a heat dissipation member for semiconductor devices and the like.
  • the laminated substrate 100 can also be said to be a temporary press-bonded body.
  • the semi-cured resin forming the composite sheet 10 is heated and melted, and pressure is applied as necessary, thereby further improving the adhesive strength with the metal layers 30 and 40. good.
  • a modified example of the laminated substrate includes an insulating sheet and a metal layer provided on the insulating sheet, and the insulating sheet is a cured product of the composite sheet described above.
  • Example 1 100 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 arc furnace under an argon atmosphere 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 ) and boron nitride (BN) 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. In this way, 20 parts by mass of the sintering aid was added to 100 parts by mass of the fired product, and mixed using a Henschel mixer to prepare powdery raw material powder.
  • the obtained compact was placed in a boron nitride container and introduced into a batch-type high-frequency furnace. In a batch-type high-frequency furnace, it was heated for 5 hours under the conditions of atmospheric pressure, nitrogen flow rate of 5 L/min, and 2000° C. (firing step). Then, it was taken out from the boron nitride container to obtain a ceramic plate.
  • the resulting ceramic plate was kept under a reduced pressure environment adjusted to 2000 Pa for 15 minutes to remove volatile components. Next, the ceramic plate was immersed in water and maintained for 30 minutes to remove solvent-soluble components. The maintenance under the reduced pressure environment and the maintenance in water were repeated, and washing was carried out twice in total (washing step). The median pore diameter of the ceramic plate thus obtained was 2.3 ⁇ m.
  • 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.
  • thermosetting resin composition contained in the semi-cured product was determined by measurement using a differential scanning calorimeter.
  • the curing rate of the impregnated thermosetting resin was 31%.
  • the filling rate of the thermosetting resin in the obtained composite sheet was 96% by volume.
  • Example 2 A composite sheet was prepared in the same manner as in Example 1, except that the number of treatments in the washing step for the ceramic plate was changed to one vacuum treatment and one water washing.
  • a measurement sample of the composite sheet was placed on a thin LED trace stand (manufactured by Tritec Co., Ltd., trade name: A2-450), and a black cylinder was placed around the measurement sample.
  • An image was then acquired from the top surface of the measurement sample with the brightness of the thin LED trace stage set to maximum intensity.
  • the acquired image is imported into image analysis software (manufactured by GNU General Public License, trade name: GIMP), converted to gray scale, the brightness threshold is confirmed in 255 steps, and the step from black to white is 230. , binarization processing was performed to prepare a binarized image.
  • FIG. 3 and FIG. 4 respectively show a grayscale image of the surface image of the measurement sample obtained in Example 1 and Comparative Example 1 and a binarized image thereof.
  • FIG. 3(a) is a grayscaled image showing the surface of the composite sheet prepared in Example 1.
  • FIG. 3(b) is a grayscaled image showing the surface of the composite sheet prepared in Comparative Example 1.
  • FIG. 4(a) is an image obtained by binarizing the image of FIG. 3(a)
  • FIG. 4(b) is an image obtained by binarizing the image of FIG. 3(b).
  • the laminate was heat-treated under conditions of 200° C. and atmospheric pressure for 2 hours to prepare a laminate substrate.
  • a heat cycle test was performed on the laminated substrate obtained by exposing the substrate to an environment of 150° C. for 30 minutes and then cooling it to an environment of ⁇ 50° C. for 30 minutes for 1,000 and 2,000 cycles. After that, using a universal testing machine (manufactured by A&D Co., Ltd., trade name: RTG-1310), JIS K 6854-1: 1999 "adhesive- A 90° peel test was carried out according to "Peel Adhesion Strength Test Method". The 90° peel test was performed at the adhesive interface between the sheet-like copper foil and the composite.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)
PCT/JP2022/031929 2021-08-26 2022-08-24 複合シート、及び複合シートの製造方法、並びに、積層基板 Ceased WO2023027123A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015124122A (ja) * 2013-12-26 2015-07-06 電気化学工業株式会社 樹脂含浸窒化ホウ素焼結体およびその用途
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体
WO2020148960A1 (ja) * 2019-01-15 2020-07-23 株式会社日本マイクロニクス プローブ基板及び電気的接続装置
WO2020203586A1 (ja) * 2019-03-29 2020-10-08 デンカ株式会社 複合体、複合体の製造方法、積層体及び積層体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015124122A (ja) * 2013-12-26 2015-07-06 電気化学工業株式会社 樹脂含浸窒化ホウ素焼結体およびその用途
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体
WO2020148960A1 (ja) * 2019-01-15 2020-07-23 株式会社日本マイクロニクス プローブ基板及び電気的接続装置
WO2020203586A1 (ja) * 2019-03-29 2020-10-08 デンカ株式会社 複合体、複合体の製造方法、積層体及び積層体の製造方法

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