WO2016043331A1 - 電着液、メタルコア基板およびメタルコア基板の製造方法 - Google Patents

電着液、メタルコア基板およびメタルコア基板の製造方法 Download PDF

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Publication number
WO2016043331A1
WO2016043331A1 PCT/JP2015/076804 JP2015076804W WO2016043331A1 WO 2016043331 A1 WO2016043331 A1 WO 2016043331A1 JP 2015076804 W JP2015076804 W JP 2015076804W WO 2016043331 A1 WO2016043331 A1 WO 2016043331A1
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Prior art keywords
electrodeposition
film
substrate
metal core
pdms
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English (en)
French (fr)
Japanese (ja)
Inventor
裕介 青木
幹人 狩野
和彦 笠野
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Mie University NUC
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Mie University NUC
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Priority to EP15842098.4A priority Critical patent/EP3196263B1/en
Priority to KR1020177007001A priority patent/KR102494877B1/ko
Priority to US15/511,470 priority patent/US20170292029A1/en
Publication of WO2016043331A1 publication Critical patent/WO2016043331A1/ja
Anticipated expiration legal-status Critical
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass 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
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3731—Ceramic materials or glass
    • 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
    • H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic 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
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3736—Metallic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49822—Multilayer substrates
    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/44—Manufacturing insulated metal core circuits or other insulated electrically conductive core circuits
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/142—Metallic substrates having insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1147—Sealing or impregnating, e.g. of pores
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
    • H05K2203/1333—Deposition techniques, e.g. coating
    • H05K2203/135—Electrophoretic deposition of insulating material

Definitions

  • the present invention relates to an electrodeposition liquid, a metal core substrate, and a method for manufacturing the metal core substrate.
  • a metal core substrate in which aluminum nitride is coated on a carbon substrate by an electrophoretic electrodeposition method (electrodeposition method) using polyimide as a binder (see, for example, Patent Document 1).
  • electrophoretic electrodeposition method electrophoretic electrodeposition method
  • a heat treatment of 300 ° C. or more is necessary. Due to the difference in thermal expansion coefficient between the conductive substrate and the ceramic layer, the substrate is warped after coating. Problems such as peeling of the conductive substrate and the ceramic layer, and generation of cracks in the ceramic layer. Therefore, it is difficult to form a ceramic layer having high thermal conductivity and high insulation on a conductive substrate.
  • coating is performed using a carbon substrate having a smaller thermal expansion coefficient than that of metal.
  • Patent Document 1 uses a carbon substrate, there is a problem in that the heat dissipation performance of the metal substrate is lower than when a metal substrate is used.
  • the use temperature of the substrate coated with the conductive substrate is limited by the heat resistance of the resin layer, so that the metal core substrate has high thermal conductivity and high insulation. There is a problem that it is difficult to get.
  • An object of the present invention is to provide a metal core substrate having high thermal conductivity and high insulation, an electrodeposition liquid used for manufacturing the metal core substrate, and a method for manufacturing the metal core substrate.
  • an electrodeposition liquid according to one embodiment of the present invention is an electrodeposition liquid used in an electrophoretic electrodeposition method, and the electrodeposition liquid includes a plurality of electrodes for coating a metal substrate. Ceramic particles and a binder composed of an organopolysiloxane composition that binds the plurality of ceramic particles.
  • the metal substrate can be coated while the ceramic material as the coating material is flexibly bonded in the electrophoretic electrodeposition method. Therefore, it is possible to form a ceramic layer having excellent heat resistance and stress relaxation with respect to temperature change.
  • the organopolysiloxane composition may be a raw material for an organopolysiloxane organic / inorganic hybrid material.
  • the metal substrate can be coated while bonding ceramic particles more firmly by using an electrodeposition liquid having a heat-resistant organopolysiloxane organic / inorganic hybrid material as a binder. Therefore, a ceramic layer (insulating layer) excellent in heat resistance and stress relaxation against temperature change can be formed.
  • a metal core substrate is a metal core substrate including a metal substrate and an insulating layer formed over the metal substrate, and the insulating layer includes a plurality of insulating layers.
  • the metal core substrate has a thermal conductivity of 2 W / mK or more and a dielectric breakdown electric field strength of 50 kV / mm or more, and the metal core substrate.
  • the heat resistant temperature is 200 ° C. or higher.
  • the metal substrate can be coated while the ceramic material as the coating material is flexibly coupled. Therefore, a metal core substrate having high thermal conductivity and high insulation can be provided.
  • the binder may be composed of a cured body of an organopolysiloxane composition.
  • ceramic particles can be flexibly bonded by using an electrodeposition solution containing an organopolysiloxane composition having heat resistance. Therefore, a ceramic layer (insulating layer) excellent in heat resistance and stress relaxation against temperature change can be formed.
  • the cured body of the organopolysiloxane composition may be composed of an organopolysiloxane organic / inorganic hybrid material.
  • ceramic particles can be more firmly bonded by using an organopolysiloxane organic / inorganic hybrid material having heat resistance as a binder. Therefore, a ceramic layer (insulating layer) excellent in heat resistance and stress relaxation against temperature change can be formed.
  • the insulating layer may be selectively formed on the metal substrate.
  • the heat radiation efficiency can be further improved.
  • the metal substrate may include a wiring layer on the insulating layer.
  • an electronic circuit board having excellent high thermal conductivity and high insulation can be provided.
  • a method of manufacturing a metal core substrate includes a step of forming an electrodeposition liquid including a plurality of ceramic particles and a binder that bonds the plurality of ceramic particles. And selectively forming an insulating layer composed of the plurality of ceramic particles on the surface of the metal substrate by an electrophoretic electrodeposition method using the electrodeposition liquid.
  • the surface shape of the electrodeposition film is uniform, and even when the metal core substrate on which the electrodeposition film is formed is bent, the electrodeposition film is not peeled off and has flexibility. Therefore, a metal core substrate having high thermal conductivity and high insulation can be manufactured.
  • the insulating layer may be selectively formed by the electrophoretic electrodeposition method using a current having a current density determined depending on the molecular weight of the binder. Good.
  • the hardness and heat resistance of the electrodeposited film are controlled by controlling the proportion of the binder contained in the electrodeposited film by electrophoretic electrodeposition using an electric current having an appropriate current density according to the molecular weight of the binder. You can control gender.
  • a step of forming a wiring layer on the insulating layer by adhesion through an electrodeposition film may be included.
  • the wiring layers can be bonded together through the uncured and semi-cured electrodeposition film, and then the wiring layers can be formed by adhesion accompanying the curing of the binder material.
  • a method of manufacturing a metal core substrate includes a step of plasma electrolytic oxidation of a surface of a metal substrate, and a surface of the metal substrate subjected to plasma electrolytic oxidation with a binder.
  • a metal core substrate having higher thermal conductivity and higher insulation can be manufactured. Therefore, a metal core substrate suitable for use as an electronic circuit substrate can be manufactured.
  • the present invention it is possible to provide a metal core substrate having high thermal conductivity and high insulation and a method for manufacturing the metal core substrate.
  • FIG. 1 is a cross-sectional view showing the structure of the metal core substrate according to the first embodiment.
  • FIG. 2 is a flowchart showing a manufacturing process of the metal core substrate according to the first embodiment.
  • 3A is a schematic configuration diagram of the electrodeposition apparatus according to Embodiment 1.
  • FIG. 3B is a diagram showing a step of forming an electrodeposition film according to Embodiment 1.
  • FIG. 4 is a diagram for explaining the characteristics of the binder according to the first embodiment.
  • FIG. 5 is a diagram showing a procedure for creating the electrodeposition liquid according to the first embodiment.
  • FIG. 6 is a diagram showing the structure of the binder raw material and the cured body thereof according to the first embodiment.
  • FIG. 7 is a diagram showing a state of the electrodeposited film surface according to the first embodiment.
  • FIG. 8 is a diagram showing an apparatus for evaluating thermal conductivity according to the first embodiment.
  • FIG. 9 is a diagram showing a change in the thermal conductivity of the electrodeposited film according to Embodiment 1.
  • FIG. 10 is a diagram showing an apparatus for evaluating the withstand voltage of an electrodeposited film according to the first embodiment.
  • FIG. 11 is a table summarizing the characteristics of the hardness, thermal conductivity, and dielectric breakdown field strength of the electrodeposition film for the metal core substrate according to the first embodiment.
  • FIG. 12 is a diagram showing a measurement result of the hardness of the electrodeposition film obtained when the current condition during electrodeposition is changed for the metal core substrate according to the present embodiment.
  • FIG. 12 is a diagram showing a measurement result of the hardness of the electrodeposition film obtained when the current condition during electrodeposition is changed for the metal core substrate according to the present embodiment.
  • FIG. 13 shows the measurement result (FIG. 13 (a)) of the hardness of the electrodeposited film obtained when the current condition during electrodeposition was changed for the metal core substrate according to the present embodiment, and the estimation. It is a figure which shows the component amount ((b) of FIG. 13) of the binder in the electrodeposition film
  • FIG. 14 is a diagram showing the deposition rate of the binder component in the electrodeposition film obtained when the current condition during electrodeposition is changed for the metal core substrate according to the present embodiment.
  • FIG. 15 is a diagram showing the measurement results of the heat resistance of the electrodeposition film obtained when the current conditions during electrodeposition are changed for the metal core substrate according to the present embodiment.
  • FIG. 16 is a diagram showing an evaluation method (estimation method) of the composition ratio of the electrodeposited film.
  • FIG. 17 is a diagram showing a detailed method of “estimation of alumina / binder ratio (weight ratio) by TG” shown in FIG.
  • FIG. 18 is a diagram showing a detailed method of “measurement of density of electrodeposited film by Archimedes method” shown in FIG.
  • FIG. 19 shows the volume ratio of the electrodeposited film calculated from the “alumina / binder ratio (weight ratio) by TG” shown in FIG. 17 and the “density of the electrodeposited film by Archimedes method” shown in FIG. It is a figure which shows an example.
  • FIG. 20 is a diagram showing an example of the structure change of the electrodeposition film when the addition amount of ES-PDMS in the electrodeposition liquid is changed.
  • FIG. 20 is a diagram showing an example of the structure change of the electrodeposition film when the addition amount of ES-PDMS in the electrodeposition liquid is changed.
  • FIG. 21 is a diagram showing an example of the structural change of the electrodeposition film when the molecular weight of ES-PDMS in the electrodeposition liquid is changed.
  • FIG. 22 is a diagram showing a comparison result between an estimated value and an actual measurement value of the thermal conductivity of the metal core substrate obtained by using the Bruggeman equation.
  • FIG. 23 is a diagram showing characteristics of a metal core substrate manufactured using various electrodeposition solutions.
  • FIG. 24 is a graph showing a part of the measurement results related to “thermal conductivity (W / mK)” among the measurement results shown in FIG.
  • FIG. 25 is a graph showing a part (including the added measurement result) of the measurement result regarding “heat-resistant temperature (3% weight reduction temperature) (° C.)” among the measurement results shown in FIG.
  • FIG. 26 is a diagram showing measured values of relative dielectric constants of electrodeposited films of two types of metal core substrates according to the present embodiment, estimated values of alumina occupation ratios obtained using the measured values, and the like.
  • FIG. 27 is a diagram showing a plasma electrolytic oxidation (PEO) film according to the second embodiment.
  • FIG. 28 shows the characteristics of the electrodeposited film after plasma electrolytic oxidation according to the second embodiment.
  • FIG. 29A is a diagram showing a PEO surface before sealing treatment according to Embodiment 2.
  • FIG. 29B is a diagram showing the PEO surface after the sealing treatment according to Embodiment 2.
  • FIG. 29C is a diagram showing a PEO surface after the sealing treatment according to Embodiment 2.
  • FIG. 30 is a diagram showing the breakdown electric field strength in each film according to the second embodiment.
  • FIG. 31 is a diagram showing thermal conductivity and dielectric strength voltage in each film according to the second embodiment.
  • FIG. 32 is a diagram showing the thermal conductivity before and after the sealing process according to the second embodiment.
  • FIG. 1 is a cross-sectional view showing the structure of the metal core substrate according to the present embodiment.
  • the metal core substrate 1 includes a metal substrate 10 and an insulating layer 12.
  • a wiring layer 14 is formed on the insulating layer 12 of the metal core substrate 1, and the circuit substrate 2 is configured by the metal core substrate 1 and the wiring layer 14.
  • the metal substrate 10 is made of, for example, an aluminum substrate.
  • the insulating layer 12 is made of alumina, for example, and is formed on the surface of the metal substrate 10 by electrodeposition. That is, the metal substrate 10 is coated with the insulating layer 12. This metal surface coating can be selectively performed on the substrate by using a photolithography technique.
  • a wiring layer 14 made of, for example, copper is formed on the insulating layer 12 by patterning.
  • FIG. 2 is a flowchart showing the manufacturing process of the metal core substrate according to the present embodiment.
  • the manufacturing method of the metal core substrate according to the present embodiment includes (1) a manufacturing method of forming an electrodeposition film on the metal substrate 10 by electrophoretic deposition, and (2) forming a plasma electrolytic oxide film on the metal substrate 10. Then, there are two types of manufacturing methods in which sealing treatment is performed by electrophoretic electrodeposition.
  • an aluminum substrate as the metal substrate 10 is prepared and cleaned. (Step S10). Thereafter, an electrodeposition film (insulating layer 12) is formed on the aluminum substrate by the above-described electrophoretic electrodeposition method (step S12).
  • the electrodeposition solution used in the electrophoresis electrodeposition method is prepared in advance. Further, when forming the electrodeposition film, a part of the aluminum substrate may be exposed from the electrodeposition film in order to improve the heat dissipation efficiency.
  • a layer formed by electrophoretic electrodeposition is called an electrodeposition film.
  • the wiring layer 14 is formed on the electrodeposition film (insulating layer 12) (step S14). Thereby, the circuit board 2 is completed.
  • the wiring layer 14 can also be formed by bonding through a semi-cured electrodeposition film and then bonding with the curing of the binder material.
  • a manufacturing method in which a plasma electrolytic oxide film is formed on the metal substrate 10 in (2) and then a sealing treatment is performed by electrophoretic electrodeposition as shown in FIG.
  • An aluminum substrate which is the substrate 10 is prepared and cleaned (step S10).
  • plasma electrolytic oxidation is performed on the aluminum substrate to form a plasma electrolytic oxide film (PEO film) (step S22).
  • a sealing process is performed to form an electrodeposition film on the surface of the plasma electrolytic oxide film by the above-described electrophoretic electrodeposition method (step S23).
  • a part of the aluminum substrate may be exposed from the electrodeposition film in order to improve the heat dissipation efficiency.
  • the wiring layer 14 is formed on the plasma electrolytic oxide film (insulating layer 12) subjected to the sealing treatment (step S14). Thereby, the circuit board 2 is completed.
  • FIG. 3A is a schematic configuration diagram of the electrodeposition apparatus according to the present embodiment.
  • FIG. 3B is a diagram illustrating a process of forming an electrodeposition film according to the present embodiment.
  • FIG. 4 is a diagram for explaining the characteristics of the binder.
  • FIG. 5 is a diagram showing a procedure for creating an electrodeposition liquid according to the present embodiment.
  • the formation of the insulating layer 12 on the metal substrate 10 is performed by an electrophoretic electrodeposition method.
  • the electrophoretic electrodeposition method is performed in an electrodeposition apparatus 20 described below.
  • the electrodeposition apparatus 20 includes a container 22, an electrodeposition liquid 28 put in the container 22, electrodes 10a and 10b immersed in the electrodeposition liquid 28, and electrodes 10a and 10b. And a connected power source 26.
  • the electrode 10a is made of, for example, an aluminum substrate.
  • the electrode 10b is made of a stainless steel material or a carbon material. A positive voltage is applied to the electrode 10a, and a negative voltage is applied to the electrode 10b. Therefore, the electrode 10a is an anode and the electrode 10b is a cathode.
  • the electrodes 10a and 10b are referred to as an aluminum substrate 10a and a SUS substrate 10b, respectively.
  • alumina particles 28a which are an example of ceramic particles, are suspended.
  • the alumina particles 28a are negatively charged in the solution.
  • the alumina particles 28a are attracted to the aluminum substrate 10a which is an anode by applying an electric field, and fixed or deposited on the aluminum substrate 10a.
  • the raw material component of the organic / inorganic hybrid material electrodeposited together with the alumina particles 28a is in an uncured or semi-cured state, and then cured by hydrolysis and polycondensation reaction in the presence of water. It becomes an inorganic hybrid material and functions as a binder 28b in the electrodeposition film as shown in FIG.
  • the aluminum substrate 10a becomes the metal substrate 10 in the metal core substrate 1, and the ceramic layer composed of the alumina particles 28a and the binder 28b formed in a layered manner attached to the surface of the aluminum substrate 10a is a metal core. It becomes the insulating layer 12 of the substrate 1.
  • the insulating layer 12 is formed in the surface facing the SUS board
  • the electrodeposition liquid 28 is created by the creation procedure shown in FIG.
  • spherical alumina Al 2 O 3 (alumina particles 28a) is prepared.
  • the alumina particles 28a are dried at 130 ° C. for 2 hours. Thereafter, dehydrated isopropyl alcohol (IPA) and monochloroacetic acid (MCAA) as a stabilizer are added.
  • the electrodeposition liquid 28 at this time is, for example, 15 wt% ⁇ -alumina (Sumitomo Chemical Sumitomo Random AA-05) having a purity greater than 99.9% and an average particle size of 0.5 ⁇ m, and MCAA (Wako Pure Chemicals Chlorocetic). Acid) is blended with 12.75 wt% and dehydrated IPA (Wako Pure Chemicals 2-propanol (super dehydrated)) is blended with 72.25 wt%.
  • IPA isopropyl alcohol
  • MCAA monochloroacetic acid
  • the ultrasonic homogenizer treatment with Hielcher UP100H for 3 minutes and the ultrasonic bath treatment with Fine FU-3H for 1 hour are performed. Done. These treatments are performed while stirring the dehydrated IPA and MCAA containing the alumina particles 28a so that the alumina particles 28a are uniformly mixed in the dehydrated IPA and MCAA.
  • a binder raw material is added to dehydrated IPA and MCAA containing the alumina particles 28a.
  • An organopolysiloxane composition is used as the binder raw material. More specifically, for example, a mixed solution of a metal alkoxide such as alkoxysilane and an organopolysiloxane having a terminal metal alkoxide (metal alkoxide-modified organopolysiloxane) is used.
  • This liquid mixture is called a raw material liquid of an organopolysiloxane PDMS (polydimethylsiloxane) hybrid, and after the raw material comes into contact with water, a cured organopolysiloxane formed by hydrolysis and dehydration polycondensation is used as an organopolysiloxane.
  • Called polysiloxane organic / inorganic hybrid material By using a flexible and heat-resistant organopolysiloxane organic / inorganic hybrid material as a binder, a ceramic layer (insulating layer) excellent in heat resistance and stress relaxation with respect to temperature change can be formed.
  • an ethyl silicate terminal modified with a weight average molecular weight (hereinafter also simply referred to as molecular weight) of 8000 which is an organopolysiloxane having an ethyl silicate (ES) terminal as shown in FIG.
  • ES-PDMS-A ethylsilicate terminal-modified PDMS
  • ES-PDMS-B ethylsilicate terminal-modified PDMS
  • ES-PDMS-C ethylsilicate terminal-modified PDMS
  • ES-PDMS-D a hybrid material containing ethyl silicate terminal-modified PDMS
  • ES-PDMS-D ethyl silicate
  • a cured product obtained by hydrolysis / dehydration polycondensation of these organopolysiloxane compositions is a cured product crosslinked through silica nanoglass 29 as shown in FIG. 6B, that is, an organopolysiloxane organic / inorganic hybrid material. It becomes.
  • ES-PDMS-A ES-PDMS-B, ES-PDMS-C, and ES-PDMS-D (collectively referred to as ES-PDMS) is, for example, as follows. .
  • Industrial product ES45) and PDMS Momentive Performance Materials Japan product YF3800 (mass average molecular weight 6000) or XF-3905 (mass average molecular weight 20000), YF-3057 (mass average molecular weight 40000)) in a screw tube bottle Stir for 30 minutes using a magnetic stirrer.
  • TTE titanium tetraethoxide
  • MA DL-malic acid diethyl ester
  • the reaction of the mixed solution at this time can be confirmed using a Fourier transform infrared spectrophotometer (FT-IR) and gel permeation chromatography (GPC).
  • FT-IR Fourier transform infrared spectrophotometer
  • GPC gel permeation chromatography
  • the above-mentioned mixed liquid of TTE and MA is prepared by putting TTE and MA in the same mole in a screw tube bottle and stirring at 25 ° C. for 30 minutes (see Example 1 of WO2010 / 143357 (Patent Document 2)).
  • ES-PDMS-D the blending conditions and production conditions were the same as for ES-PDMS-B, but the polymerization treatment was carried out at 130 ° C. for 24 hours.
  • the step of adding the binder material to the dehydrated IPA and MCAA containing the alumina particles 28a is performed while stirring the dehydrated IPA and MCAA containing the alumina particles 28a, as shown in FIG.
  • the electrodeposition solution is created as described above.
  • an electrodeposition film (insulating layer 12) is formed on the aluminum substrate 10a by an electrodeposition method.
  • the electrodeposition method is performed by the electrodeposition apparatus 20 shown in FIG. 3A.
  • the power supply used was Protech 3900 manufactured by Anatech.
  • the electrodeposition conditions are such that the current is constant and, for example, the electrodeposition time is appropriately adjusted so that the film thickness of the electrodeposition film is 50 ⁇ m.
  • a heat treatment is performed at 250 ° C. for 2 hours to obtain an electrodeposition cured film obtained by curing the electrodeposition film.
  • the properties of the electrodeposited film subjected to the heat treatment at 250 ° C. for 2 hours have been described. For example, a cured product can be obtained even at other temperature conditions from room temperature to 300 ° C. I can do it.
  • the thermal expansion coefficient differs between the aluminum substrate 10a and the electrodeposition film of alumina
  • the difference in the thermal expansion coefficient between aluminum and alumina is reduced by using the organopolysiloxane hybrid described above as the binder material.
  • a polymer (organopolysiloxane organic / inorganic hybrid material) obtained by heating modified ES-PDMS has high heat resistance (continuous 200 ° C., short time 400 ° C. or higher) and flexibility, and this is used as a binder.
  • An alumina electrodeposition film also has high heat resistance.
  • FIG. 7 is an optical microscope image showing the state of the surface of the electrodeposition film formed on the aluminum substrate 10a. As shown in FIG. 7, it can be seen that the surface shape of the electrodeposition film is uniform. Further, even when the metal core substrate 1 on which the electrodeposition film is formed is bent, the electrodeposition film is not peeled off and has flexibility.
  • the effect of the addition of modified ES-PDMS to the electrodeposition solution on the properties of the electrodeposition film will be described.
  • the influence of the addition of the modified ES-PDMS to the electrodeposition liquid on the properties of the electrodeposition film is due to the difference in the molecular weight of the modified ES-PDMS and the modified ES-PDMS. Varies depending on the amount added.
  • FIG. 8 is a diagram showing a thermal conductivity evaluation apparatus according to the present embodiment.
  • the evaluation apparatus 30 includes a heater 32, an aluminum block 34, a sample 36, an aluminum block 34, and air cooling fins 38 on a heat insulating material 31. Further, heat radiation grease is applied between the heater 32, the aluminum block 34, the sample 36, the aluminum block 34, and the air cooling fins 38. A hole is made in each of the two aluminum blocks 34, a thermocouple is inserted, and the temperature T1 on the heater 32 side and the temperature T2 on the air cooling fin 38 side are measured.
  • the thermal resistance is measured.
  • the measured thermal resistances are the aluminum block 34 (half), the sample 36, the thermal resistance of the aluminum block 34 (half), the contact thermal resistance between the aluminum block 34 (half) and the sample 36, and the aluminum block.
  • 34 is the total contact thermal resistance between sample 34 and sample 36.
  • the thermal resistance of the sample 36 can be obtained by measuring the thermal resistance in the same manner without the sample 36 and subtracting the thermal resistance other than the sample 36 and the contact thermal resistance from the total thermal resistance. Further, the thermal conductivity of the sample 36 is obtained from the thickness and area of the sample 36.
  • thermal conductivity when the metal core substrate 1 is used as the sample 36 is shown below.
  • FIG. 9 is a diagram showing changes in the thermal conductivity of the electrodeposited film according to the present embodiment.
  • the electrodeposited film thermal conductivity decreases.
  • the electrodeposited film thermal conductivity increases. This is because the electrodeposition film becomes dense due to a decrease in current density, and the occupation ratio of alumina in the electrodeposition film increases. Therefore, the thermal conductivity of the electrodeposited film can be increased by reducing the electrodeposition current density during electrodeposition.
  • the current density is too low, it is difficult to form a uniform electrodeposition film on the entire substrate, and it is preferable to reduce the electrodeposition current density to the extent that a uniform electrodeposition film can be obtained.
  • FIG. 10 is a diagram showing an apparatus for evaluating the electric field strength of the electrodeposited film according to the present embodiment.
  • the dielectric breakdown electric field strength evaluation apparatus 40 includes a lower electrode 42, a measurement sample 44, an upper electrode 46, and a power supply 48 in a container.
  • a fluorine-containing inert liquid such as 3M product Fluorinert (registered trademark) is placed, and the lower electrode 42, the measurement sample 44, and the upper electrode 46 are arranged in this order in the fluorine-based inert liquid. Is done.
  • a power supply 48 is connected between the lower electrode 42 and the upper electrode 46.
  • the lower electrode 42 and the upper electrode 46 are made of, for example, a flat plate made of stainless steel.
  • the upper electrode 46 has, for example, a flat portion with a diameter of 10 mm ⁇ and an end curvature of 10 mm.
  • the size of the lower electrode 42 is a size on which the measurement sample 44 can be placed, and is, for example, 50 mm ⁇ .
  • the maximum voltage that can be applied between the lower electrode 42 and the upper electrode 46 from the power supply 48 is 10 kV. In the dielectric breakdown electric field strength evaluation apparatus 40, the voltage applied between the lower electrode 42 and the upper electrode 46 is gradually increased, and when a current of 5.0 mA or more flows, the dielectric film breakdown is assumed.
  • the measurement specimen 44 was used as the metal core substrate 1, and the dielectric breakdown electric field strength of the metal core substrate 1 was measured.
  • the dielectric strength voltage is 3 when the film thickness of the electrodeposition film is 35 ⁇ m.
  • a characteristic of 4 kV and a dielectric breakdown electric field strength of 98 kV / mm was obtained.
  • FIG. 11 is a diagram summarizing the characteristics of the hardness of the electrodeposited film, the thermal conductivity, and the breakdown field strength of the metal core substrate 1 according to the present embodiment.
  • the hardness of the electrodeposition film is a scratch hardness.
  • the hardness of the electrodeposited film is measured by, for example, a scratch hardness meter (MODEL318-S manufactured by ERICHSEN).
  • ES ethyl silicate
  • ES-PDMS modified ES-PDMS-A, modified ES-PDMS- Comparison is made with respect to the metal core substrate 1 when an electrodeposition film is formed on the aluminum substrate 10a with respect to a PDMS hybrid in which the blending amount of B or modified ES-PDMS-C modified) is 15 parts by weight.
  • the hardness is 2.0N for modified ES-PDMS-A, 2.0N for modified ES-PDMS-B, and 1.0N for modified ES-PDMS-C.
  • ES-PDMS-A or ES-PDMS-B In this case, it can be seen that a particularly high strength electrodeposition film is formed.
  • the thermal conductivity is 2.4 W / mK for modified ES-PDMS-A, 2.9 W / mK for modified ES-PDMS-B, 1.1 W / mK for modified ES-PDMS-C, and has a molecular weight of 22000. It can be seen that an electrodeposition film having the highest thermal conductivity is sometimes produced.
  • the dielectric breakdown electric field strength was 76.0 kV / mm for modified ES-PDMS-A, 97.1 kV / mm for modified ES-PDMS-B, 30.9 kV / mm for modified ES-PDMS-C, and a molecular weight of 22000. It can be seen that an electrodeposited film having the highest dielectric breakdown electric field strength was produced at the time.
  • the blending amount of modified ES is 5 parts by weight
  • the hardness is 2.0 N when the blending amount of ES-PDMS-A is 15 parts by weight, and 3.3 N when the blending amount of ES-PDMS-A is 17.5 parts by weight. It can be seen that a higher strength electrodeposition film is produced when the PDMS content is higher.
  • the thermal conductivity when the blending amount of ES-PDMS-A is 15 parts by weight, it is 2.4 W / mK, and when the blending amount of ES-PDMS-A is 17.5 parts by weight, it is 3.1 W / It can be seen that an electrodeposition film having a higher thermal conductivity is produced when the blending amount of ES-PDMS-A is mK.
  • modified ES was blended in 5 parts by weight and 7.5 parts by weight, and the blended amount of ES-PDMS-A was 17 parts.
  • the metal core substrate 1 when an electrodeposition film is formed on the aluminum substrate 10a as 5 parts by weight will be compared.
  • the hardness is 3.3 N when the blending amount of ES is 5 parts by weight, and 3.5 N when the blending amount of ES is 7.5 parts by weight.
  • the thermal conductivity is 3.1 W / mK when the blending amount of ES is 5 parts by weight, and 2.2 W / mK when the blending amount of ES is 7.5 parts by weight.
  • the blending amount of ES It can be seen that an electrodeposition film having a higher thermal conductivity is produced when the value is lower.
  • the dielectric breakdown electric field strength is 79.5 kV / mm when the blending amount of ES is 5 parts by weight, and 89.1 kV / mm when the blending amount of ES is 7.5 parts by weight. It can be seen that an electrodeposition film having a higher dielectric breakdown field strength is produced when the amount is higher.
  • the molecular weight of the main chain PDMS is smaller than 8000 (modified ES-PDMS-A)
  • the stress relaxation property of the electrodeposited film is insufficient and the warpage of the substrate tends to be large.
  • the molecular weight of the main chain PDMS exceeds 80,000, the modified PDMS component is likely to be separated in the electrodeposition solution, which is not suitable for forming a uniform electrodeposition film. From the above results, the molecular weight of the modified ES-PDMS is preferably about 8000 to 80,000.
  • the thermal expansion of aluminum and alumina is achieved.
  • the difference in rate can be reduced.
  • the polymer obtained by heating the modified ES-PDMS has high heat resistance (continuous 200 ° C., short time 400 ° C. or higher) and flexibility. Therefore, in the metal core substrate 1, an electrodeposition film having high thermal conductivity and withstand voltage (insulation withstand voltage) can be obtained.
  • An electrodeposition film prepared with an electrodeposition solution containing 5 parts by weight of ES and 15 parts by weight of ES-PDMS-B was stored at 300 ° C. for 200 hours, but there was no change in thermal conductivity, withstand voltage, and adhesive strength. It has been confirmed that it has resistance to rapid cooling from 300 ° C. to room temperature and rapid heat shock.
  • a metal wiring layer can be formed on the metal core substrate 1 using an uncured electrodeposition film as an adhesive layer.
  • an aluminum substrate (A2017S) having a length of 80 mm, a width of 20 mm, and a thickness of 2 mm degreased with ethanol and acetone and a copper plate having a length of 80 mm, a width of 20 mm, and a thickness of 0.2 mm, 5 parts by weight of ES,
  • An electrodeposition film having a thickness of 25 ⁇ m is formed by an electrodeposition solution to which 15 parts by weight of modified ES-PDMS having a molecular weight of 22000 is added.
  • the adhesion strength between the copper plate and the aluminum plate was determined in accordance with JIS K6850, a method for testing the tensile shear bond strength of rigid substrates, using a tensile testing machine (Shimadzu Corporation precision universal testing machine Autograph AGS-J).
  • the adhesive strength (MPa) is calculated by pulling the end of each aluminum plate in the opposite direction at a test speed of 5 mm / min and dividing the stress when the adhesive surface peels by the adhesive area (20 mm ⁇ 20 mm). It has been confirmed that the strength is, for example, 0.5 MPa (1.8 MPa or the like).
  • the characteristic evaluation (measurement) of the metal core substrate 1 was performed in more detail. Influence on the structure of the electrodeposition film by the current conditions during electrodeposition 4-2. Influence on heat resistance of electrodeposited film by current conditions during electrodeposition 4-3. Measurement of composition ratio of electrodeposited film 4-4. This will be described as a study on dielectric characteristics.
  • FIG. 12 is a diagram showing measurement results for the hardness of the electrodeposition film obtained when the current conditions (current values) during electrodeposition were changed for various metal core substrates 1 according to the present embodiment.
  • the combination of the blending amount (g) of ES and the blending amount (g) and molecular weight (Mw) of ES-PDMS contained in the PDMS hybrid contained in the electrodeposition liquid used for the production of the metal core substrate 1 is different.
  • 6 shows the measurement results regarding the hardness of the electrodeposition film of the metal core substrate 1 obtained by electrodeposition at 5A, 7.5A, 10A, and 12A.
  • the compounding quantity (g) has shown the compounding quantity with respect to 100g of electrodeposition liquid.
  • “ ⁇ ” indicates that cracks occurred in all of the electrodeposited films prepared under the conditions, and “ ⁇ ” indicates that cracks occurred in some of the electrodeposited films.
  • “ ⁇ ” indicates that no crack was generated in all the electrodeposition films, and the numerical value (N) described together with “ ⁇ ” or “ ⁇ ” indicates the measured hardness.
  • FIG. 13 shows the measurement results of the hardness of the electrodeposition film obtained when the current conditions (current density) during electrodeposition were changed for the various metal core substrates 1 according to the present embodiment ((a 14) and the estimated component amount of the binder in the electrodeposition film ((b) of FIG. 13).
  • FIG. 13A is a graph in which the hardness (measured value) shown in FIG. 12 is plotted as a graph showing the relationship between the current density (A / cm 2 ) and the hardness (N) during electrodeposition. It is. However, some measurement results are added to the measurement results shown in FIG. The four types of curves correspond to combinations (four types) of the blending amount (g) and molecular weight (Mw) of ES-PDMS constituting the PDMS hybrid contained in the used electrodeposition liquid.
  • FIG. 13B shows the binder (resin) contained in the electrodeposition film obtained by using five types of electrodeposition liquids having different combinations of ES-PDMS blending amount (g) and molecular weight (Mw). The weight ratio (%; estimated value) is shown.
  • the following can be seen regarding the relationship between the molecular weight of ES-PDMS and the hardness of the electrodeposited film. That is, when the molecular weight of ES-PDMS is small, the hardness of the electrodeposited film increases and cracks are likely to occur. On the other hand, when the molecular weight of ES-PDMS is large, the hardness of the electrodeposited film becomes small and cracks are hardly generated. Further, if the current during electrodeposition is increased, the electrodeposition film can be made porous and stress can be relaxed. As a result, an electrodeposited film free from cracks can be formed (that is, because it is porous, thermal conductivity is reduced).
  • FIG. 14 shows the deposition rate of the binder component (estimated value) in the electrodeposition film obtained when the current conditions (current or voltage) during electrodeposition are changed for various metal core substrates 1 according to the present embodiment.
  • the deposition rate of the binder component varies depending on the difference in the molecular weight of ES-PDMS constituting the PDMS hybrid contained in the electrodeposition solution.
  • the deposition rate of the binder component is considered to increase at a low current.
  • Influence on alumina component Alumina particles have a particle size distribution. That is, when the current during electrodeposition is small, small alumina particles are easily electrodeposited. Further, as the amount of current increases, relatively large amounts of large alumina particles are deposited.
  • alumina particles having a narrow particle size distribution are deposited under a low current condition, and deposits are performed under a condition having a wide particle size distribution under a high current condition.
  • electrophoresis conditions differ between ES and ES-PDMS. That is, it is considered that low molecular weight ES is more easily deposited even under low current conditions than high molecular weight ES-PDMS. Therefore, the ratio between ES and ES-PDMS as the binder component may differ depending on the current conditions, but the difference in density due to the difference in molecular weight is slight (range 1.04-1.2). In the composition evaluation of the electrodeposited film, it is assumed that the same as the non-electrodeposited film even when the current conditions are different.
  • FIG. 15 is a diagram showing the measurement results of the heat resistance of the electrodeposition film obtained when the current conditions (current density) at the time of electrodeposition are changed for the various metal core substrates 1 according to the present embodiment.
  • . 15A shows the temperature at which the weight of the electrodeposition film is reduced by 3% (3% weight reduction temperature (° C.))
  • FIG. 15B shows the weight of the electrodeposition film at 600 ° C. The reduction ratio (weight reduction @ 600 ° C. (%)) is shown.
  • the five types of curves are combinations of the blending amount (g) and molecular weight (Mw) of ES-PDMS constituting the PDMS hybrid contained in the used electrodeposition liquid ( 5 types).
  • FIG. 16 is a diagram showing an evaluation method (estimation method) of the composition ratio of the electrodeposited film. That is, FIG. 16A is a schematic diagram showing the structure of the electrodeposited film, and FIG. 16B is a flowchart showing a composition ratio estimation method.
  • the electrodeposition film is composed of alumina, a binder, and pores (air).
  • the alumina / binder ratio (weight ratio) is estimated by thermogravimetric analysis (TG), while the density of the electrodeposited film is measured by Archimedes method. From the obtained alumina / binder ratio (weight ratio) and the density of the electrodeposited film, the volume ratio of alumina, binder and pores shown in the electrodeposited film was estimated.
  • FIG. 17 is a diagram showing a detailed method of “estimation of alumina / binder ratio (weight ratio) by TG” shown in FIG.
  • FIG. 17 (a) the weight loss when each of the electrodeposited film containing alumina and the binder, the electrodeposited film of alumina only, and the cured body of the bander is heated to 1000 ° C.
  • Measure. (A) of FIG. 17 is a figure which shows the measurement result.
  • the amount of weight loss (residual weight (%)) due to temperature dependence of the electrodeposited film including, is shown on the right.
  • ES + ES-PDMS ” indicates the weight loss (residual weight (%)) depending on the temperature.
  • FIG. 17B is a diagram showing a method for estimating the weight ratio.
  • FIG. 18 is a diagram showing a detailed method of “density measurement of electrodeposited film by Archimedes method” shown in FIG.
  • FIG. 18 shows an outline of the Archimedes method apparatus and an equation for calculating the density.
  • the density ds of the object ⁇ mass w / (w ⁇ mass w ′ to be balanced when the object is in liquid) ⁇ ⁇ (the liquid in which the object is immersed) Density d1) is shown.
  • FIG. 18B shows a calculation example of the binder and electrodeposition film density calculated by the method shown in FIG.
  • the binder density is 1.1 g / m 3
  • the electrodeposition film density is 3.30 ⁇ 0.03 g / m 3 is shown.
  • FIG. 19 shows the volume ratio of the electrodeposited film calculated from the “alumina / binder ratio (weight ratio) by TG” shown in FIG. 17 and the “density of the electrodeposited film by Archimedes method” shown in FIG. It is a figure which shows an example.
  • an electrodeposition formed of an electrodeposition solution containing a PDMS hybrid in which ES and ES-PDMS having a molecular weight Mw of 22000 are blended at ES: ES-PDMS 5: 15.
  • Examples of the weight ratio (wt%), density (g / cm 3 ), and volume ratio (%) of alumina, binder and pores constituting the film and the electrodeposition film are shown.
  • FIG. 20 is a diagram showing an example of the structural change of the electrodeposition film when the addition amount of ES-PDMS in the electrodeposition solution is changed.
  • An example of (c) of FIG. 20 is shown.
  • the molecular weight Mw of the used ES-PDMS is 6000
  • the blending amount with ES (ES: ES-PDMS) is 4 types of 5: 5, 5:10, 5:15, 5:20.
  • FIG. 21 is a diagram showing an example of a structural change (change in volume ratio) of the electrodeposition film when the molecular weight of ES-PDMS in the electrodeposition liquid is changed.
  • examples of volume ratios (%) of components of various electrodeposition films actually measured by the method shown in FIGS. 16 to 19 are shown.
  • the results for ES-PDMS with a molecular weight of 8000 and 22000 are shown.
  • FIG. 22 is a diagram showing a comparison result between an estimated value and an actual measurement value of the thermal conductivity of the electrodeposited film obtained using the Bruggeman equation.
  • the thermal conductivity of a composite (compound) composed of two components, a filler and a matrix, is shown by the Bruggeman equation in FIG.
  • FIG. 22B is a diagram showing the relationship between the volume filling rate (%) of alumina and the thermal conductivity (W / mK) of the electrodeposited film made of alumina-binder.
  • FIG. 22 is a diagram showing a comparison between the two actually measured values and the theoretical values (estimated values) shown in (b) of FIG.
  • the measured value is smaller than the estimated value of the thermal conductivity of the electrodeposited film obtained using the Bruggeman equation. This is considered to be due to the influence of pores contained in the electrodeposition film.
  • the electrodeposited film obtained using ES-PDMS having a higher molecular weight has a large accumulation of pore components, and thus the measured value is significantly different from the theoretical value (estimated value). Become.
  • FIG. 23 is a diagram showing characteristics of the metal core substrate 1 manufactured using various electrodeposition liquids. This figure corresponds to the measurement result added to the measurement result shown in FIG. 11. From the left, “Type of ES-PDMS” (molecular weight of ES-PDMS mixed in electrodeposition solution) , “ES45 blending amount (part)” (ES blending amount), “ES-PDMS blending amount (part)”, “hardness (N)” of the obtained electrodeposition film, “thermal conductivity (W / mK) ) ”,“ Dielectric breakdown (electric field) strength (kV / mm) ”,“ Heat resistant temperature (3% weight reduction temperature) (° C.) ”,“ Binder component weight ratio (wt%) shown in composite ”,“ Alumina ” “Volume ratio (%)”, “Binder volume ratio (%)”, and “Vole (air) volume ratio (%)” are shown.
  • “Type of ES-PDMS” molecular weight of ES-PDMS mixed in electrodeposition solution
  • the heat resistance tends to be improved by increasing the molecular weight of ES-PDMS. This is because the proportion of the binder component that occupies the electrodeposition film decreases due to the increase in the molecular weight of ES-PDMS.
  • the occupation ratio (volume filling factor) of alumina is 58% in order for the thermal conductivity of the composite to be 2.0 W / mK or more.
  • the occupation ratio (volume filling factor) of alumina must be 65% or more.
  • the thermal conductivity of the composite decreases.
  • the porosity is low (5% or less)
  • the relationship between the thermal conductivity ke of the composite at the porosity f and the thermal conductivity km of the base material is that small spherical vacancies are uniformly dispersed.
  • the regarded Bruggeman equation ke / km (1-f) 3/2
  • the porosity is preferably 5% or less.
  • the alumina occupancy is 65% or more.
  • composites are produced in which the proportions of alumina and pores (air) occupying the composite are 65% or more and 5% or less, respectively.
  • FIG. 24 is a graph showing a part of the measurement results related to “thermal conductivity (W / mK)” among the measurement results shown in FIG.
  • the addition amount (horizontal axis (g)) of PDMS blended as a PDMS hybrid (5 g ES and ES-PDMS) contained in 100 g of the electrodeposition solution, and the metal core substrate formed of the electrodeposition solution The relationship with thermal conductivity (vertical axis (W / mK)) is plotted.
  • the binder amount is further decreased. Since the electrodeposition condition is a large current condition, the electrodeposition film is considered to be easily porous. As a result, the thermal conductivity decreases.
  • FIG. 25 is a graph showing a part (including the added measurement result) of the measurement result regarding “heat resistance temperature (3% weight loss temperature) (° C.)” among the measurement results shown in FIG.
  • the addition amount (horizontal axis (g)) of PDMS blended as a PDMS hybrid (5 g of ES and PDMS) contained in 100 g of the electrodeposition solution, and the heat resistance of the electrodeposition film formed with the electrodeposition solution The relationship with temperature (3% weight loss temperature) (° C.) is plotted.
  • FIG. 26 is a diagram showing measured values of relative dielectric constants of electrodeposited films of two types of metal core substrates 1 according to the present embodiment, estimated values of alumina occupation ratios obtained using the measured values, and the like. More specifically, FIG. 26A is a graph showing measured values at 1 kHz of the relative dielectric constant of the electrodeposited films of the two types of metal core substrates 1 according to the present embodiment. FIG. 26B is a relational expression based on the effective medium theory used to obtain the alumina occupation ratio in the electrodeposited film from the measured values shown in FIG. (C) in FIG. 26 shows the measured values (“relative permittivity”) shown in (a) of FIG.
  • the metal core substrate according to the present embodiment is It turns out that it is useful also as a board
  • the metal core substrate according to the present embodiment it is possible to form an insulating heat dissipation substrate having high heat resistance and thermal shock resistance. That is, by using an electrodeposition liquid that is flexible and has a heat-resistant polydimethylsiloxane organic / inorganic hybrid material as a binder, it is possible to form a ceramic layer that is excellent in heat resistance and stress relaxation with respect to temperature change.
  • the metal core substrate according to the present embodiment is (1) the ceramic layer does not peel even when bent, (2) has a heat resistance of 300 ° C., and has a stress relaxation property that can withstand a thermal shock from room temperature to 300 ° C. (3) High insulation (3.0 kV / 50 um), (4) High heat dissipation (2.5 W / mK), (5) Wiring layer can be attached by adhesion via electrodeposition film It can be seen which features are possible. As an example, a metal core substrate having a thermal conductivity of 2 W / mK or higher, a dielectric breakdown electric field strength of 50 kV / mm or higher, and a heat resistant temperature of 200 ° C. or higher is realized.
  • the binder material has been described using an organopolysiloxane organic / inorganic hybrid material as an example, but other materials may be used.
  • it may be a cured product of an organopolysiloxane composition containing an organopolysiloxane organic / inorganic hybrid material.
  • metal alkoxide terminal-modified organopolysiloxane ethyl silicate terminal-modified organopolydimethylsiloxane (ES-PDMS) was shown, but other metal alkoxide terminal-modified organopolysiloxane can be used.
  • the metal alkoxide terminal-modified organopolysiloxane has one or both ends of the main chain of the organopolysiloxane represented by the general formula (1), or at least one side of the side chain represented by the general formula (2), (3) or (4 ) Or a hydrolysis condensate thereof.
  • organopolysiloxane for example, polydialkyl siloxane, polydiaryl siloxane, polyalkylaryl siloxane and the like are preferably mentioned. More specifically, polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, And polydiphenyldimethylsiloxane. One of these may be used, or two or more may be used in combination.
  • alkoxysilane which modifies at least one terminal or side chain of the organopolysiloxane and at least a part thereof, but alkoxysilane is particularly preferable.
  • alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-
  • alkoxysilanes may be used, or two or more types may be used in combination.
  • alkoxysilane tetramethoxysilane and trimethoxymethylsilane are particularly preferable.
  • organopolysiloxane polydimethylsiloxane and polydiphenyldimethylsiloxane are particularly preferable.
  • a polydimethylsiloxane or polydiphenyldimethylsiloxane having a terminal modified with methoxysilane can be suitably produced.
  • alkoxysilane hydrolysis condensate examples include polymethyl silicate, polyethyl silicate, polypropoxy silicate, polybutoxy silicate, and polybutoxy silicate.
  • One of these alkoxysilane hydrolysis condensates may be used, or two or more may be used in combination.
  • ethyl silicate is particularly preferable.
  • the organopolysiloxane is preferably polydimethylsiloxane or polydiphenyldimethylsiloxane as described above.
  • the metal substrate 10 is not limited to the above-described aluminum substrate, and other conductive substrates may be used, and examples thereof include metal substrates such as copper and SUS steel, carbon substrates, and the like.
  • the ceramic particles are not limited to the alumina particles 28a described above, but may be other ceramic materials such as AlN, MgO, and SiC.
  • FIG. 27 is a diagram showing a plasma electrolytic oxidation (PEO) apparatus according to the present embodiment.
  • FIG. 28 is a diagram showing the characteristics of the PEO film according to the present embodiment.
  • PEO plasma electrolytic oxidation
  • the plasma electrolytic oxidation (PEO) method is a technique in which plasma is generated in an aqueous solution and a thin oxide film on the aluminum surface is discharged and broken by a micro arc to form a new oxide film.
  • the PEO device 50 includes an anode electrode 55a, a cathode electrode 55b, and a power source 58 that are made of an aluminum substrate.
  • a voltage of 600 V, for example, is applied between the anode electrode 55a and the cathode electrode 55b.
  • a voltage of about 40 V is applied between the two aluminum substrates 10a and the SUS substrate 10b.
  • a metal substrate that has undergone plasma electrolytic oxidation has higher hardness, corrosion resistance, heat resistance, and insulation than a metal substrate that does not undergo plasma electrolytic oxidation, such as ceramics.
  • the hardness is 30 to 100 Hv for an aluminum substrate not subjected to PEO, whereas it is 800 to 1400 Hv for a substrate subjected to PEO.
  • an aluminum substrate not subjected to PEO has a corrosion resistance of about 100 hours, whereas a substrate subjected to PEO has a corrosion resistance of about 5000 hours.
  • the instantaneous heat resistance is about 640 ° C. for an aluminum substrate not subjected to PEO, and about 2000 ° C. for a substrate subjected to PEO.
  • the insulating property is 0 for an aluminum substrate not subjected to PEO, whereas it is 2.5 kV at a thickness of 50 ⁇ m for a substrate subjected to PEO.
  • the plasma electrolytic oxide film (PEO film) formed by PEO is an oxide film having high wear resistance and high corrosion resistance.
  • the PEO film has high mechanical strength, it becomes porous due to the gas generated during the film formation, so that the surface roughness is large and the insulating property may be inferior.
  • the PEO film has a thermal conductivity of 1 W / mK or less and a withstand voltage of 2.5 kV or less. Therefore, for use as an electronic circuit board, it is effective to perform a sealing treatment in which an electrodeposition film is formed on the plasma electrolytic oxide film in order to enhance thermal conductivity and insulation.
  • the electrophoretic electrodeposition method described above is used to form the electrodeposition film. That is, the aluminum substrate 10a in FIG. 3A is used as an aluminum substrate on which a PEO film is formed, and an electrodeposition film is formed on the PEO film.
  • the conditions for electrodeposition are such that the current is constant and, for example, the electrodeposition time is appropriately adjusted so that the film thickness of the electrodeposition film is 50 ⁇ m.
  • a heat treatment is performed at 250 ° C. for 2 hours to cure the electrodeposition film. Thereby, an electrodeposition cured film is obtained.
  • FIG. 29A is a diagram showing the surface of the PEO film before the sealing treatment according to the embodiment.
  • 29B and 29C are diagrams showing the surface of the PEO film after the sealing treatment according to the embodiment.
  • the PEO film before the sealing treatment has a much finer film than the anodic oxide film, but has an uneven shape due to holes.
  • the PEO film after the sealing treatment in which the electrodeposition film having a thickness of 5 ⁇ m is formed on the surface by the electrodeposition liquid to which 5 parts by weight of ES and 15 parts by weight of PDMS-B are added as shown in FIG.
  • the holes are sealed, and the uneven shape on the surface of the PEO film is smoother than in FIG. 29A.
  • the pores are sealed as shown in FIG. 29C, and the PEO film is further compared with FIGS. 29A and 29B.
  • the uneven shape on the surface of the film is smooth. Therefore, it can be seen that the pore treatment on the surface of the PEO film is eliminated and the surface is smoothed by the sealing treatment.
  • FIG. 30 is a diagram showing the breakdown electric field strength in each film according to the embodiment.
  • FIG. 31 is a diagram showing thermal conductivity and dielectric strength voltage in each film according to the embodiment.
  • FIG. 32 is a diagram showing the thermal conductivity before and after the sealing treatment according to the embodiment.
  • FIG. 30 shows the breakdown electric field strength for a PEO film of 50 ⁇ m, a film obtained by forming an electrodeposition film of 13 ⁇ m on the PEO film of 50 ⁇ m, and only the electrodeposition film of 35 ⁇ m. As shown in FIG. 30, the breakdown electric field strength is increased by forming an electrodeposition film on the PEO film.
  • each film shown in FIG. 30 (“PEO film (PEO film 50 ⁇ m)”, “Electrodeposition film according to the present technique (only 35 ⁇ m of electrodeposition film)”, “PEO sealed with an electrodeposition film” Insulation withstand voltage and thermal conductivity of a film (film in which an electrodeposition film of 13 ⁇ m is formed on a PEO film of 50 ⁇ m) ”.
  • the thermal conductivity of the “PEO film” is 0.89 W / mK
  • the thermal conductivity of the “electrodeposition film according to the present technology” is 2.56 W / mK
  • the thermal conductivity of the “PEO film sealed with the film” is 1.71 W / mK.
  • the thermal conductivity of the PEO film portion is increased by about 10% (this description will be described later with reference to FIG. 32).
  • the dielectric strength voltage after the PEO film sealing treatment is 3.8 kV, and assuming that the dielectric constant of the electrodeposited film portion is not different from that of the PEO film, the shared voltage of the PEO film when the breakdown voltage is applied is approximately 3. 1 kV. Therefore, it can be seen that the withstand voltage of the PEO film is increased by 25% by the sealing treatment as compared with the insulation withstand voltage of the PEO film before the sealing treatment is 2.5 kV.
  • the PEO film before sealing treatment has a thermal conductivity of 0.89 W / mK (see FIG. 31), but after the electrodeposition film is formed and sealed.
  • the thermal conductivity of the entire film is 1.71 W / mK (see FIG. 31)
  • the thermal conductivity of the PEO film is 0.98 W / mK
  • the thermal conductivity of the electrodeposited film is 2. 54 W / mK. Therefore, it can be seen that the thermal conductivity of the PEO layer is increased by 10% by sealing the PEO film.
  • the heat resistance of the metal core substrate 1 and the stress relaxation property against temperature change can be improved by performing the sealing treatment.
  • the metal core substrate according to the present embodiment after forming the PEO film, by performing the sealing treatment, it is possible to form an insulating heat dissipation substrate with more excellent high heat resistance and thermal shock resistance.
  • the binder material added to the electrodeposition liquid has been described using an organopolysiloxane organic / inorganic hybrid material as an example, but other materials may be used.
  • it may be a cured product of an organopolysiloxane composition containing a polydimethylsiloxane organic / inorganic hybrid material.
  • the metal substrate 10 is not limited to the above-described aluminum substrate, and a conductive substrate such as another metal substrate or a carbon substrate may be used.
  • the ceramic particles are not limited to the alumina particles described above, and may be other ceramic materials.
  • composition of the material constituting the electrodeposition liquid is not limited to 15 wt% ⁇ -alumina, 12.75 wt% MCAA, and 72.25 wt% dehydrated IPA, but may be other blends.
  • the metal core substrate according to the present invention is, for example, an inverter substrate, a headlight light source, a quick charger, a heat pump air conditioner, solar light and a heat appliance, etc., to devices and apparatuses that require high heat resistance, thermal shock resistance, and high insulation. Available.
  • Electrodeposition apparatus 1 Metal Core Board 2 Circuit Board 10 Metal Board (Aluminum Board) 10a electrode (aluminum substrate) 10b Electrode (SUS substrate) 12 Insulating layer (electrodeposition film) DESCRIPTION OF SYMBOLS 14 Wiring layer 20 Electrodeposition apparatus 22 Container 26, 48, 58 Power supply 28 Electrodeposition liquid 28a Alumina particle (ceramic particle) 28b Binder 29 Silica nano glass 30 Evaluation device 31 Heat insulating material 32 Heater 34 Aluminum block 36 Sample 38 Air-cooled fin 40 Dielectric breakdown field strength evaluation device 42 Lower electrode 44 Measurement sample 46 Upper electrode 50 PEO device 55a Anode electrode 55b Cathode electrode

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JP6722568B2 (ja) * 2016-11-17 2020-07-15 サンコール株式会社 半導体素子取付用基板端子板の製造方法
JP6414260B2 (ja) 2017-03-23 2018-10-31 三菱マテリアル株式会社 放熱回路基板
JP6902266B2 (ja) * 2017-07-13 2021-07-14 国立大学法人三重大学 セラミック基板の製造方法、及びパワーモジュールの製造方法
JP7011303B2 (ja) * 2017-10-02 2022-01-26 国立大学法人三重大学 反射基板の製造方法および電着液
US10790731B2 (en) * 2018-05-30 2020-09-29 General Electric Company Methods of depositing coatings on electrical machine components
CN111172578B (zh) * 2020-01-17 2021-07-06 深圳市裕展精密科技有限公司 金属制品及其制备方法
CN113861693B (zh) * 2021-10-24 2022-07-19 扬州晨化新材料股份有限公司 一种汽车用过电泳耐高温密封胶及其制备方法
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EP3196263A1 (en) 2017-07-26
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