WO2022255450A1 - Feuille de résine, stratifié et dispositif semi-conducteur - Google Patents

Feuille de résine, stratifié et dispositif semi-conducteur Download PDF

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Publication number
WO2022255450A1
WO2022255450A1 PCT/JP2022/022489 JP2022022489W WO2022255450A1 WO 2022255450 A1 WO2022255450 A1 WO 2022255450A1 JP 2022022489 W JP2022022489 W JP 2022022489W WO 2022255450 A1 WO2022255450 A1 WO 2022255450A1
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WIPO (PCT)
Prior art keywords
resin sheet
boron nitride
melt viscosity
nitride particles
laminate
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PCT/JP2022/022489
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English (en)
Japanese (ja)
Inventor
翔平 水野
亜希 高麗
圭吾 大鷲
雄輝 金島
Original Assignee
積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN202280036578.5A priority Critical patent/CN117397371A/zh
Priority to JP2023525911A priority patent/JPWO2022255450A1/ja
Priority to KR1020237041134A priority patent/KR20240017803A/ko
Publication of WO2022255450A1 publication Critical patent/WO2022255450A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a resin sheet, a laminate comprising a cured product of the resin sheet, and a semiconductor device comprising the laminate.
  • Patent Document 1 discloses a method for manufacturing an insulating sheet in which two resin sheets containing an aggregate containing boron nitride and an epoxy resin are laminated and hot-pressed to form an insulating layer.
  • Patent Document 1 describes an invention relating to a method for producing an insulating sheet characterized by adjusting the relationship between the thickness before and after hot pressing and the viscosity at 175°C within a specific range. It is shown that an insulating sheet having excellent thermal conductivity and insulating properties can be obtained by this manufacturing method.
  • an object of the present invention is to provide a resin sheet having excellent insulating properties and thermal conductivity, and excellent adhesion to a metal plate.
  • the present inventors have made intensive studies in order to achieve the above object.
  • the above problem is solved by a resin sheet containing a binder resin and boron nitride particles, wherein the content of the boron nitride particles, the porosity in the cross section of the resin sheet, and the melt viscosity ratio are set to specific ranges.
  • the present invention relates to the following [1] to [14].
  • Melt viscosity ratio [Maximum melt viscosity from 40°C to 195°C (Pa s)]/[Average melt viscosity from 40°C to 100°C (Pa s)] [2]
  • the inorganic filler other than the boron nitride particles is at least one selected from the group consisting of alumina, aluminum nitride, magnesium oxide, diamond, and silicon carbide.
  • [7] A cured product of the resin sheet according to any one of [1] to [6] above.
  • [8] A cured product of the resin sheet according to [7] above, which has a thermal conductivity of 10 W/(m ⁇ K) or more.
  • [9] A cured product of the resin sheet according to [7] or [8] above, a metal base plate, and a metal plate, wherein the cured resin sheet and the metal plate are provided on the metal base plate.
  • Laminates provided in this order.
  • the laminate according to the above [9] wherein the laminate is a circuit board.
  • [11] The laminate according to the above [9] or [10], wherein the metal plate has a circuit pattern.
  • a semiconductor device comprising the laminate according to any one of [9] to [11] above, and a semiconductor element provided on the metal plate.
  • a method for manufacturing a laminate comprising a cured product of a resin sheet, a metal base plate, and a metal plate, wherein the cured product of the resin sheet and the metal plate are provided in this order on the metal base plate, ,
  • the semi-cured resin sheet has a cross-sectional porosity of 0.01% or more and 2.0% or less,
  • the present invention it is possible to provide a resin sheet that is excellent in insulation and thermal conductivity, as well as excellent adhesion to a metal plate.
  • FIG. 1 is a schematic cross-sectional view showing a semiconductor device according to one embodiment of the present invention.
  • FIG. It is an explanatory view explaining a method of tensile shear measurement.
  • the cross-sectional porosity of the resin sheet of the present invention is 0.01% or more and 2.0% or less. If the porosity is more than 2.0%, the ratio of air in the resin sheet increases and the insulating properties deteriorate. On the other hand, if the porosity is less than 0.01%, a phenomenon in which the resin flows out to the side (resin flow) is likely to occur when a metal plate is laminated on the resin sheet, and the insulating properties deteriorate. . From the viewpoint of facilitating suppression of resin flow, the cross-sectional porosity of the resin sheet is preferably 0.05% or more, more preferably 0.1% or more. It is 8% or less, more preferably 1.6% or less.
  • the porosity in the cross section of the resin sheet means the ratio of the area of the voids to the area of the cross section when the cross section of the resin sheet is observed with a scanning electron microscope (SEM). measured by the method
  • SEM scanning electron microscope
  • the melt viscosity ratio of the resin sheet of the present invention is 2 or more. If the melt viscosity ratio is less than 2, the adhesion when laminating the metal plate on the resin sheet is deteriorated. From the viewpoint of improving adhesion, the melt viscosity ratio of the resin sheet is preferably 4 or more, more preferably 6 or more. Although the upper limit of the melt viscosity ratio is not particularly limited, the melt viscosity ratio of the resin sheet is usually 20 or less. The melt viscosity ratio can be adjusted to a desired value by adjusting the conditions for producing the resin sheet described later, specifically the press pressure, press time, press temperature, etc. of the curable resin composition. .
  • the melt viscosity ratio is obtained by the following formula in melt viscosity measurement where the temperature is increased from 40 ° C. to 195 ° C. at a rate of 8 ° C./min. )] / [average melt viscosity from 40 ° C. to 100 ° C. (Pa s)] Specifically, using a rheometer measuring device (manufactured by TA instruments, "ARES"), melting at each temperature under the conditions of an angular velocity of 40 rad/sec, a measurement temperature of 40 to 195 ° C., and a heating rate of 8 ° C./min. Measure the viscosity and determine the melt viscosity ratio. The average melt viscosity at 40 ° C.
  • the binder resin contained in the resin sheet of the present invention is not particularly limited, but is preferably a thermosetting resin. resins, thermosetting polyimide resins, amino alkyd resins, and the like.
  • the binder resin used for the resin sheet may be used singly or in combination of two or more.
  • epoxy resin is preferable among those mentioned above.
  • Epoxy resins include, for example, compounds containing two or more epoxy groups in the molecule.
  • the epoxy resin has a weight average molecular weight of less than 5,000, for example.
  • Specific examples of epoxy resins include styrene skeleton-containing epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, phenol novolac-type epoxy resins, biphenol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-type epoxy resins, anthracene-type epoxy resins, epoxy resins having an adamantane skeleton, epoxy resins having a tricyclodecane skeleton, and epoxy resins having a triazine nucleus in the skeleton, and gly
  • the epoxy equivalent of the epoxy resin is not particularly limited, it is, for example, 70 g/eq or more and 500 g/eq or less.
  • the epoxy equivalent of the epoxy resin is preferably 80 g/eq or more, and preferably 400 g/eq or less, more preferably 350 g/eq or less.
  • an epoxy equivalent can be measured according to the method prescribed
  • the epoxy resins described above may be used singly or in combination of two or more.
  • the content of the binder resin in the resin sheet is not particularly limited, but is preferably 10% by volume or more, more preferably 15% by volume or more, and preferably 50% by volume or less, more preferably 40% by volume or less. be.
  • the content of the binder resin is at least these lower limits, it is possible to sufficiently bind the inorganic filler such as boron nitride particles after curing to obtain a sheet having a desired shape. If the content of the binder resin is not more than these upper limits, a certain amount or more of inorganic filler such as boron nitride particles can be contained, so that it is possible to improve thermal conductivity while improving insulation. can.
  • the binder resin contained in the resin sheet is cured by a curing agent to bind inorganic fillers such as boron nitride particles. That is, the resin sheet according to the present invention preferably further contains a curing agent.
  • curing agents include phenol compounds (phenol heat curing agents), amine compounds (amine heat curing agents), imidazole compounds, acid anhydrides, and the like. Among these, imidazole compounds are preferred. Curing agents may be used singly or in combination of two or more.
  • phenol compounds include novolac-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.
  • Amine compounds include dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.
  • imidazole compounds include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 -methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'- Methylimidazolyl-(1′)]
  • Acid anhydrides include styrene/maleic anhydride copolymer, benzophenonetetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, 4,4′-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol.
  • the content of the curing agent relative to the binder resin is not particularly limited as long as the binder resin can be appropriately cured on a volume basis, but is, for example, 0.1 or more and 0.8 or less.
  • the content of the curing agent to the binder resin is preferably 0.15 or more, more preferably 0.2 or more, and preferably 0.6 or less, more preferably 0.5 or less, on a volume basis.
  • the resin sheet of the present invention contains boron nitride particles.
  • the content of the boron nitride particles in the resin sheet is 30% by volume or more and 80% by volume or less.
  • the content of the boron nitride particles is less than 30 volumes, the thermal conductivity of the resin sheet tends to decrease.
  • the content of the boron nitride particles exceeds 80% by volume, the amount of the binder resin is so small that it becomes difficult to obtain a desired shape of the resin sheet and its cured product.
  • the content of boron nitride particles in the resin sheet is preferably 40% by volume or more, more preferably 50% by volume or more, and preferably 75% by volume or less, more preferably 70% by volume or less.
  • the average length of the primary particles of the boron nitride particles is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, still more preferably 2.0 ⁇ m or more, and more preferably 20 ⁇ m or less, and more preferably It is 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the average aspect ratio determined by the major axis and minor axis of the primary particles of boron nitride particles is preferably 1 or more, more preferably 2 or more, and preferably 7 or less, more preferably 6 or less.
  • the average aspect ratio and average major axis are obtained from the major axis and minor axis of the primary particle diameter of the boron nitride particles measured in the cross section exposed by the cross-section polisher. Specifically, it is as follows. First, a cross-section of the cured resin sheet is exposed by a cross-section polisher, and the exposed cross-section is observed with a scanning electron microscope (SEM) at a magnification of 400 to 1200 to obtain an observed image. In the observation image, using image analysis software, the major diameter and minor diameter of the primary particles of 200 boron nitride particles are randomly measured, and the aspect ratio of each particle is calculated from the major diameter / minor diameter. Let the average value of 1 be the average aspect.
  • SEM scanning electron microscope
  • the average value of the major diameters of the measured 200 primary particles is defined as the average major diameter.
  • the major diameter is the length of the longest portion of the observed primary particles of the boron nitride particles in the observation image.
  • the minor axis is the length in the direction perpendicular to the major axis direction in the observed image.
  • the boron nitride particles preferably comprise boron nitride agglomerate particles.
  • Agglomerated boron nitride particles are aggregated particles formed by aggregating primary particles.
  • Boron nitride agglomerated particles can generally be determined whether they are agglomerated particles, for example, by cross-sectional observation with an SEM.
  • the aggregated boron nitride particles may maintain the shape of the aggregated particles, or may be deformed, disintegrated, or crushed through various processes such as press molding.
  • the aggregated boron nitride particles are subjected to a process such as press molding, so that even if they are deformed, collapsed, crushed, etc., they are generally not oriented, and they exist in a certain amount of aggregation. Therefore, for example, by observing the cross section described above, it is suggested that the particles are boron nitride agglomerated particles, and it can be determined whether or not they are agglomerated particles.
  • the aggregated boron nitride particles mixed in the resin sheet preferably have an average particle size of 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of effectively improving insulation and thermal conductivity. It is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the average particle size of aggregated particles can be measured by a laser diffraction/scattering method. Regarding the method of calculating the average particle size, the particle size (d50) of aggregated particles when the cumulative volume is 50% is adopted as the average particle size.
  • the method for producing the aggregated boron nitride particles is not particularly limited, and can be produced by a known method. For example, it can be obtained by aggregating (granulating) primary particles prepared in advance, and specific examples thereof include a spray drying method and a fluid bed granulation method.
  • the spray drying method also called spray drying
  • the spray drying method can be classified into a two-fluid nozzle method, a disk method (also called a rotary method), an ultrasonic nozzle method, etc., and any of these methods can be applied.
  • the granulation step is not necessarily required as a method for producing aggregated boron nitride particles.
  • boron nitride crystals crystallized by a known method grow, the primary particles of boron nitride naturally aggregate to form agglomerated particles.
  • aggregated boron nitride particles include “UHP-G1H” manufactured by Showa Denko KK, “HP-40” manufactured by Mizushima Ferroalloy Co., Ltd., and the like.
  • the resin sheet of the present invention may contain an inorganic filler other than the boron nitride particles in addition to the boron nitride particles described above.
  • an inorganic filler other than boron nitride particles a thermally conductive filler may be used.
  • the thermally conductive filler has, for example, a thermal conductivity of 10 W/(m ⁇ K) or more, preferably 15 W/(m ⁇ K) or more, more preferably 20 W/(m ⁇ K) or more.
  • the upper limit of the thermal conductivity of the thermally conductive filler is not particularly limited, it may be, for example, 300 W/(m ⁇ K) or less, or 200 W/(m ⁇ K) or less.
  • Inorganic fillers other than boron nitride particles can enter the gaps between boron nitride particles, such as boron nitride agglomerated particles, to further increase thermal conductivity.
  • the thermal conductivity of the inorganic filler can be measured, for example, by a periodic heating thermoreflectance method using a thermal microscope manufactured by Bethel Co., Ltd. on a cross section of the filler cut by a cross section polisher.
  • the inorganic filler other than boron nitride particles is preferably at least one selected from the group consisting of alumina, aluminum nitride, magnesium oxide, diamond, and silicon carbide.
  • alumina is preferable among the above from the viewpoint of preventing deterioration of insulating properties while improving thermal conductivity and adhesion to a metal plate.
  • inorganic fillers other than boron nitride particles one type may be used alone, or two or more types may be used in combination.
  • the inorganic filler other than the boron nitride particles may be of any shape, and may be scaly, spherical, crushed, amorphous, polygonal, or aggregated particles.
  • the inorganic filler other than the boron nitride particles preferably has an average aspect ratio of primary particles of 3 or less. Examples of such fillers include spherical fillers. Spherical alumina is more preferable as the spherical filler.
  • the average aspect ratio of primary particles can be measured by cross-sectional observation as described above.
  • the average aspect ratio of inorganic fillers other than boron nitride particles is more preferably 2 or less.
  • the inorganic filler other than boron nitride particles may have an aspect ratio of 1 or more.
  • the use of inorganic fillers other than boron nitride particles having such a low aspect ratio makes it easier to improve thermal conductivity and adhesion to metal plates.
  • the average particle size of the inorganic filler other than the boron nitride particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more. Also, it is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less. When the average particle size is less than these upper limits, it becomes easier to mix the inorganic filler in the resin sheet at a high filling rate. Moreover, when it is more than a lower limit, it will become easy to improve insulation.
  • the average particle size of inorganic fillers other than boron nitride particles can be measured, for example, by the Coulter Counter method. Inorganic fillers other than boron nitride particles may be used singly or in combination of two or more.
  • the content of inorganic fillers other than boron nitride particles in the resin sheet is, for example, 2% by volume or more and 55% by volume or less. By adjusting the content to such a value, for example, thermal conductivity and adhesion to the metal plate can be further enhanced.
  • the content of inorganic fillers other than boron nitride particles in the resin sheet is preferably 4% by volume or more, more preferably 10% by volume or more, and the content of inorganic fillers other than boron nitride particles is preferably 55% by volume. %, and more preferably 45% by volume or less from the viewpoint of making it easier to ensure thermal conductivity by containing a certain amount or more of boron nitride particles.
  • the volume ratio of the inorganic filler other than boron nitride particles to the boron nitride particles is, for example, 0.005 or more 4 It is below. By setting it within this range, it becomes easier to suppress the deterioration of the insulation due to heating while further increasing the thermal conductivity and the adhesion to the metal plate. From such a viewpoint, the ratio is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.3 or more, and preferably 3 or less, more preferably 2 or less, and further preferably 1 or less.
  • the total content of the boron nitride particles and the inorganic filler other than the boron nitride particles in the resin sheet is preferably 65% by volume or more. When it is 65 volumes or more, it is possible to ensure even higher heat dissipation performance. Further, the total content of the boron nitride particles and the inorganic filler other than the boron nitride particles in the resin sheet is preferably 80% by volume or less. By making it 80% by volume or less, the adhesion of the resin sheet to the metal plate is further improved. From such a viewpoint, the content of the inorganic filler is preferably 78% by volume or less, more preferably 75% by volume or less, and even more preferably 70% by volume or less.
  • the resin sheet according to the present invention contains a dispersant, a curing accelerator, a coupling agent such as a silane coupling agent, a flame retardant, an antioxidant, an ion scavenger, a tackifier, a plasticizer, Other additives such as thiso-imparting agents and colorants may also be included.
  • the thickness of the resin sheet of the present invention is not particularly limited, it is, for example, 50 ⁇ m or more and 500 ⁇ m or less. When the thickness is 50 ⁇ m or more, it becomes easy to secure a certain level of insulation and heat dissipation, and when the thickness is 500 ⁇ m or less, it becomes easy to thin a circuit board or a semiconductor device, which will be described later.
  • the thickness of the insulating resin sheet is preferably 60 ⁇ m or more, more preferably 70 ⁇ m or more, and preferably 400 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the resin sheet of the present invention is formed of a curable resin composition containing a binder resin, boron nitride particles, and optionally an inorganic filler other than the boron nitride particles, a curing agent, and other additives.
  • the method of forming the resin sheet from the curable resin composition is not particularly limited, but for example, the curable resin composition is coated on a support such as a release sheet, and the dried coating is heated under predetermined conditions. press.
  • the curable resin composition may be diluted with a diluting solvent, applied to a support or the like, and dried.
  • the conditions for hot pressing may be appropriately adjusted according to the type of binder resin, the content of boron nitride particles, etc., so as to achieve a predetermined melt viscosity ratio and void ratio, and are not limited, but for example the following: should be adjusted as follows.
  • the press pressure is, for example, 5 MPa or more and 30 MPa or less, preferably 15 MPa or more and 25 MPa or less
  • the press temperature is, for example, 60° C. or more and 130° C. or less, preferably 70° C. or more and 110° C. or less
  • the press time is, for example, 20 minutes or more and 120 minutes or less, preferably 30 minutes. minutes or more and 100 minutes or less.
  • the binder resin contained in the resin sheet formed by hot pressing is in an uncured state or in a partially cured state. In this specification, the partially cured state is also referred to as a semi-cured state.
  • the specific method of hot pressing is not particularly limited, but the following method is preferable from the viewpoint of improving the manufacturing yield.
  • a sample in which a curable resin composition is applied onto a support such as a release sheet (e.g., a release PET sheet) and dried to form a coating film (a sample having a coating film formed on the support) are prepared, and a laminate is prepared by laminating the two samples so that the coating films are in contact with each other. Both surfaces of the laminate are sandwiched between two metal plates and hot-pressed. Since the resin sheet manufactured by such a method has a two-layer structure, it is possible to reduce the frequency of manufacturing a resin sheet having pinholes formed therein.
  • the resin sheet in the present invention can be cured by heating at a temperature equal to or higher than the curing temperature of the binder resin to obtain a cured product of the resin sheet. Curing is preferably carried out by heating under pressure. A cured product of the resin sheet can constitute a part of a laminate to be described later.
  • the thermal conductivity of the cured resin sheet is preferably 10 W/(m ⁇ K) or more. By setting the thermal conductivity to 10 W/(m ⁇ K) or more, the heat radiation performance is excellent, and when used as a circuit board, the heat generated by the elements mounted on the circuit board is efficiently released to the outside.
  • the thermal conductivity of the cured resin sheet is more preferably 11 W/(m ⁇ K) or higher, still more preferably 12 W/(m ⁇ K) or higher, and even more preferably 15 W/(m ⁇ K) or higher.
  • the upper limit of the thermal conductivity of the cured resin sheet is not particularly limited, but is practically about 30 W/(m ⁇ K), for example.
  • the thermal conductivity of the cured product of the resin sheet it is preferable to measure the thermal conductivity in the thickness direction by a laser flash method.
  • the laminate of the present invention comprises a metal base plate 11 and a metal plate 12 in addition to the cured resin sheet 10 of the present invention. 10 and a metal plate 12 in this order.
  • the heat conductivity thereof is preferably 10 W/m ⁇ K or more.
  • Materials used for these include metals such as aluminum, copper, gold, and silver, and graphite sheets. Aluminum, copper, or gold is preferred, and aluminum or copper is more preferred, from the viewpoint of more effectively increasing thermal conductivity.
  • the thickness of the metal base plate 11 is preferably 0.1-5 mm, and the thickness of the metal plate 12 is preferably 10-2000 ⁇ m, more preferably 10-900 ⁇ m.
  • the metal plate includes a plate such as a copper plate and a foil such as copper foil.
  • the shape of the metal base plate is not particularly limited, but it may be a flat plate shape, or a shape with a large surface area such as an uneven shape or a bellows shape.
  • the laminate 13 is preferably used as a circuit board.
  • the metal plate 12 in the laminate 13 may have a circuit pattern.
  • the circuit pattern may be appropriately patterned according to the elements to be mounted on the circuit board.
  • the circuit pattern is not particularly limited, but may be formed by etching or the like.
  • the metal base plate 11 is used as a heat sink or the like.
  • a semiconductor device 15 includes a laminate 13 having a cured resin sheet 10, a metal base plate 11, and a metal plate 12, and a semiconductor device 15 provided on the metal plate 12 of the laminate 13. and a semiconductor element 14 formed by a semiconductor device.
  • the metal plate 12 is preferably patterned by etching or the like to have a circuit pattern.
  • each semiconductor element 14 is connected to the metal plate 12 via a connection conductive portion 16 formed on the metal plate 12 .
  • the connection conductive portion 16 is preferably made of solder.
  • a sealing resin 19 is provided on the surface of the laminate 13 on the metal plate 12 side. At least the semiconductor element 14 is sealed with the sealing resin 19 , and the metal plate 12 is preferably sealed together with the semiconductor element 14 with the sealing resin 19 as necessary.
  • the semiconductor elements 14 are not particularly limited, but at least one is preferably a power element (that is, a power semiconductor element), so that the semiconductor device 15 is preferably a power module.
  • Power modules are used, for example, in inverters and the like.
  • the power module is used in industrial equipment such as elevators and uninterruptible power supplies (UPS), but the application is not particularly limited.
  • a lead 20 is connected to the metal plate 12 .
  • the lead 20 extends outside, for example, from the sealing resin 19 and connects the metal plate 12 to an external device or the like.
  • a wire 17 may be connected to the semiconductor element 14 .
  • the wires 17 may connect the semiconductor element 14 to another semiconductor element 14, the metal plate 12, the leads 20, etc., as shown in FIG.
  • the semiconductor element 14 generates heat when it is driven by being supplied with electric power through the leads 20 or the like. Heat is radiated from the plate 11 .
  • the metal base plate 11 may be connected to a heat sink made up of radiation fins or the like, if necessary.
  • the semiconductor device 15 is preferably manufactured through a reflow process in its manufacturing process. Specifically, in the manufacturing method of the semiconductor device 15, first, the laminate 13 is prepared, the connection conductive portion 16 is formed on the metal plate 12 of the laminate 13 by solder printing or the like, and the connection conductive portion 16 is formed. A semiconductor element 14 is mounted on the . After that, the laminate 13 with the semiconductor element 14 mounted thereon is passed through a reflow furnace and heated inside the reflow furnace, and the semiconductor element 14 is connected onto the metal plate 12 by the connecting conductive portions 16 . Although the temperature in the reflow furnace is not particularly limited, it is, for example, about 200 to 300.degree.
  • the semiconductor element 14 may be sealed by laminating the sealing resin 19 on the laminate 13 after the reflow process. Also, before sealing with the sealing resin 19, the wires 17, the leads 20, etc. may be appropriately attached.
  • a mode in which the semiconductor element 14 is connected to the metal plate 12 by the reflow process is shown, but the present invention is not limited to this mode. substrate (not shown).
  • Laminate manufacturing method In the case of producing a laminate comprising a cured resin sheet, a metal base plate, and a metal plate, the resin sheet is placed between the metal base plate and the metal plate, and is heated and pressed by press molding to form the metal base. It is preferable to manufacture a laminate by bonding a plate and a metal plate via a cured resin sheet.
  • the resin sheet is preferably cured by heating during press molding, but may be partially or completely cured before press molding.
  • the porosity in the cross section of the semi-cured resin sheet is 0.01% or more and 2.0% or less, and the melt viscosity is measured from 40 ° C. to 195 ° C. at a temperature increase rate of 8 ° C./min.
  • the press pressure is, for example, 5 MPa or more and 30 MPa or less, preferably 15 MPa or more and 25 MPa or less
  • the press temperature is, for example, 60° C. or more and 130° C. or less, preferably 70° C. or more and 110° C. or less
  • the time may be, for example, 20 minutes or more and 120 minutes or less, preferably 30 minutes or more and 100 minutes or less.
  • the press pressure is, for example, 0.5 MPa or more and 20 MPa or less, preferably 1 MPa or more and 10 MPa or less
  • the press temperature is, for example, 120° C. or more and 230° C. or less, preferably 140° C. or more and 220° C. or less
  • the pressing time is, for example, 30 minutes or more and 150 minutes or less, preferably 50 minutes or more and 120 minutes or less.
  • the measuring method and evaluation method of each physical property are as follows.
  • the cross section of the resin sheet produced in each example and comparative example was smoothed with abrasive paper, and an observation surface was produced with a cross section polisher (manufactured by JEOL Ltd., "IB-19500CP"). After that, the observation surface obtained by sputtering the cross section with a Pt ion sputter (E-1045, manufactured by Hitachi High-Technologies) was scanned with a scanning electron microscope (SEM) to obtain a 500-fold cross-sectional image so that the entire sheet could be included. rice field. Image processing and analysis were then performed on this image. Using "ImageJ" (developed by Wayne Rasband), the cross-sectional image was binarized into voids and other regions by the Threshold function, and the porosity was obtained from the area ratio of voids to the cross-sectional area.
  • melt viscosity ratio [Maximum melt viscosity from 40°C to 195°C (Pa s)]/[Average melt viscosity from 40°C to 100°C (Pa s)]
  • a ⁇ 2 circular electrode was formed on each laminate (6 cm ⁇ 6 cm) produced in Examples and Comparative Examples, and a voltage was applied to the electrode at a rate of 20 kV/min.
  • the voltage at which dielectric breakdown occurred in the measurement sample was defined as the dielectric breakdown voltage, and evaluation was made based on the following evaluation criteria. (Evaluation criteria) A: 2 kV or more B: less than 2 kV
  • the tensile shear measurement was performed by preparing a sample for tensile shear measurement as follows, in accordance with JIS K6850. As shown in FIG. 3, samples were prepared by laminating a copper plate 32 and a copper plate 33 on both sides of a resin sheet 31 (thickness: 0.12 mm, length L: 12.5 mm, width: 25 mm) prepared in each example and comparative example. made. Each copper plate is 100 mm long, 25 mm wide and 0.5 mm thick. At this time, as shown in FIG.
  • one end side 32a of the copper plate 32 and one end side 33a of the copper plate 33 are arranged on both sides of the resin sheet 31, and the other end sides 32b and 33b of the respective copper plates are laminated so that they are separated from each other. .
  • the sample prepared in this manner was pressed at 145° C. for 30 minutes under a pressure of 5 MPa, and then pressed at 195° C. for 55 minutes to cure the resin sheet 31 of the sample, thereby preparing a sample for tensile shear measurement.
  • the sample for tensile shear measurement was pulled in the shear direction by a tensile tester, and the maximum strength at that time was taken as the tensile shear force (MPa) and evaluated according to the following criteria.
  • thermosetting component is an epoxy resin and a phenoxy resin. They were used at a volume ratio of 7.4:2.6, respectively.
  • curing agent "HN2200”, “1B2MZ” manufactured by Showa Denko Materials Co., Ltd., and "1B2MZ” manufactured by Shikoku Kasei Co., Ltd. : used at a volume ratio of 1.1.
  • Example 1 The binder resin, inorganic filler, and curing agent shown in Table 1 were mixed in the amounts shown in Table 1 to obtain a curable resin composition.
  • the curable resin composition is applied onto a release PET sheet (40 ⁇ m thick) and dried in an oven at 50° C. for 10 minutes to form a coating film of the curable resin composition on the release PET sheet.
  • Two samples were prepared. The two samples thus prepared are laminated so that the coating films are in contact with each other to prepare a laminate, and after sandwiching the laminate between two metal plates, press pressure 18 MPa, press temperature 100 ° C., press time It was hot pressed under press melting conditions for 45 minutes. Thus, a resin sheet sandwiched between release PET sheets was obtained. Various measurements were performed using the resin sheet.
  • the release PET sheet was peeled off, and both sides of the resin sheet were sandwiched between a first metal layer (copper plate, thickness 500 ⁇ m) and a second metal layer (aluminum plate, thickness 1.0 mm), and subjected to a pressure of 5 MPa. After pressing for 30 minutes at 145° C., pressing was performed at 195° C. for 55 minutes to produce a laminate in which the first metal layer, the cured resin sheet, and the second metal layer were laminated in this order. Various measurements were performed using the laminate.
  • Examples 2 to 12 Comparative Examples 1 to 6
  • a resin sheet and a laminate were prepared in the same manner as in Example 1, except that the type and amount of each component contained in the curable resin composition and the press melting conditions were changed as shown in Tables 1 and 2, and various evaluations were performed. did

Abstract

La présente invention concerne une feuille de résine qui contient une résine liante et des particules de nitrure de bore, la teneur en particules de nitrure de bore étant de 30 à 80 % en volume, la porosité dans la section transversale de la feuille de résine étant de 0,01 à 2,0 %, et le rapport de viscosité à l'état fondu {[viscosité maximale à l'état fondu (Pa・s) de 40 °C à 195 °C]/[viscosité moyenne à l'état fondu (Pa・s) de 40 °C à 100 °C]} étant supérieur ou égal à 2 pour une mesure de viscosité à l'état fondu mesurée de 40 °C à 195 °C à une vitesse d'élévation de température de 8 °C/minute.　La présente invention peut fournir une feuille de résine ayant d'excellentes propriétés d'isolation et de conductivité thermique et une excellente adhésivité à une plaque métallique.
PCT/JP2022/022489 2021-06-04 2022-06-02 Feuille de résine, stratifié et dispositif semi-conducteur WO2022255450A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2013082873A (ja) * 2011-09-28 2013-05-09 Sekisui Chem Co Ltd Ｂステージフィルム及び多層基板
JP2013227451A (ja) * 2012-04-26 2013-11-07 Hitachi Chemical Co Ltd エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、硬化エポキシ樹脂組成物、樹脂シート、プリプレグ、積層板、金属基板、及びプリント配線板
JP2013254880A (ja) * 2012-06-08 2013-12-19 Denki Kagaku Kogyo Kk 熱伝導性絶縁シート、金属ベース基板及び回路基板、及びその製造方法
JP2019150997A (ja) * 2018-03-01 2019-09-12 積水化学工業株式会社 積層体
JP2020102556A (ja) * 2018-12-21 2020-07-02 積水化学工業株式会社 積層体、電子部品、及びインバータ

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JPS5943608U (ja) 1982-09-13 1984-03-22 国産電機株式会社 内燃機関停止装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013082873A (ja) * 2011-09-28 2013-05-09 Sekisui Chem Co Ltd Ｂステージフィルム及び多層基板
JP2013227451A (ja) * 2012-04-26 2013-11-07 Hitachi Chemical Co Ltd エポキシ樹脂組成物、半硬化エポキシ樹脂組成物、硬化エポキシ樹脂組成物、樹脂シート、プリプレグ、積層板、金属基板、及びプリント配線板
JP2013254880A (ja) * 2012-06-08 2013-12-19 Denki Kagaku Kogyo Kk 熱伝導性絶縁シート、金属ベース基板及び回路基板、及びその製造方法
JP2019150997A (ja) * 2018-03-01 2019-09-12 積水化学工業株式会社 積層体
JP2020102556A (ja) * 2018-12-21 2020-07-02 積水化学工業株式会社 積層体、電子部品、及びインバータ

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