WO2016103783A1 - Feuille adhésive thermoconductrice, son procédé de fabrication et dispositif électronique l'utilisant - Google Patents

Feuille adhésive thermoconductrice, son procédé de fabrication et dispositif électronique l'utilisant Download PDF

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Publication number
WO2016103783A1
WO2016103783A1 PCT/JP2015/073289 JP2015073289W WO2016103783A1 WO 2016103783 A1 WO2016103783 A1 WO 2016103783A1 JP 2015073289 W JP2015073289 W JP 2015073289W WO 2016103783 A1 WO2016103783 A1 WO 2016103783A1
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WIPO (PCT)
Prior art keywords
adhesive sheet
heat conductive
conductive adhesive
thermal conductivity
heat conduction
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PCT/JP2015/073289
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English (en)
Japanese (ja)
Inventor
亘 森田
邦久 加藤
豪志 武藤
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リンテック株式会社
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Priority to JP2016565952A priority Critical patent/JP6806330B2/ja
Publication of WO2016103783A1 publication Critical patent/WO2016103783A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—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
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
    • 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

Definitions

  • the present invention relates to a heat conductive adhesive sheet, and more particularly to a heat conductive adhesive sheet used for an electronic device, a method for producing the same, and an electronic device using the same.
  • thermoelectric conversion device a thermoelectric conversion device
  • photoelectric conversion device a photoelectric conversion device
  • semiconductor device such as a large-scale integrated circuit
  • thermoelectric conversion device although it is related to the above-described heat dissipation control, the heat applied to one surface of the thermoelectric element is changed in the temperature direction in the thickness direction inside the thermoelectric element.
  • Patent Document 1 discloses a thermoelectric conversion element having a structure as shown in FIG. That is, a P-type thermoelectric element 41 and an N-type thermoelectric element 42 are connected in series, thermoelectric power take-out electrodes 43 are arranged at both ends thereof to constitute a thermoelectric conversion module 46, and both sides of the thermoelectric conversion module 46 are arranged.
  • the film-like substrates 44 and 45 having flexibility and made of two kinds of materials having different thermal conductivities are provided.
  • the film-like substrates 44 and 45 are provided with materials (polyimides) 47 and 48 having low thermal conductivity on the bonding surface side with the thermoelectric conversion module 46, and on the opposite side to the bonding surface of the thermoelectric conversion module 46, High thermal conductivity materials (copper) 49 and 50 are provided so as to be located on a part of the outer surfaces of the substrates 44 and 45.
  • Patent Document 2 discloses a thermoelectric conversion module having the structure shown in FIG. 8, and an electrode 54 that also serves as a high thermal conductivity member is embedded in low thermal conductivity members 51 and 52, and these are thermoelectric elements 53. In contrast, the conductive adhesive layer 55 and the insulating adhesive layer 56 are disposed. Further, in Patent Document 3, as shown in the cross-sectional configuration diagram of the thermoelectric conversion element (the arrangement in the depth direction of the thermoelectric element 61 and the internal electrode arrangement is omitted) in FIG. An insulating base layer 65 is disposed on the surface via an adhesive layer 67 and directly on the other surface, and a pattern layer composed of a metal layer 63 and a resin layer 64 is provided on the base layer 65. Flexible substrates 62 and 66 are disclosed.
  • thermoelectric sheet having a function of selectively radiating heat and generating a temperature gradient inside the electronic device.
  • the present inventors have conducted a study by applying a heat conductive adhesive sheet composed of a high heat conductive portion and a low heat conductive portion to the thermoelectric element of the thermoelectric conversion device as described above.
  • the present inventors have found a new problem that the dimensional accuracy relating to the pattern of the high heat conduction portion and the low heat conduction portion of the sheet is poor and a predetermined temperature difference cannot be obtained.
  • the reason why the dimensional accuracy is deteriorated is a difference in internal stress including curing shrinkage or the like in the high heat conductive portion and the low heat conductive portion constituting the heat conductive adhesive sheet.
  • the present invention aims to improve the dimensional accuracy of the high heat conduction part and the low heat conduction part of the heat conductive adhesive sheet and to reduce the thermal conductivity of the low heat conduction part, and further to the electronic device via an adhesive layer. It is an object of the present invention to provide a thermally conductive adhesive sheet, a method for producing the same, and an electronic device using the same, which can be easily laminated without causing a sufficient temperature difference inside the electronic device.
  • the present inventors constituted a heat conductive adhesive sheet from a high heat conductive portion and a low heat conductive portion provided with adhesiveness, and a specific amount in the low heat conductive portion. (Vol%) hollow filler is contained, and the high heat conductive portion and the low heat conductive portion independently constitute all the thickness of the heat conductive adhesive sheet, or at least one of them is a part of the thickness of the heat conductive adhesive sheet.
  • the present inventors have found that the above-mentioned problems can be solved by using a thermally conductive adhesive sheet constituting the present invention, thereby completing the present invention. That is, the present invention provides the following (1) to (12).
  • a heat conductive adhesive sheet comprising a part of the thickness of the adhesive sheet.
  • thermosetting resin is a silicone resin or a urethane resin.
  • thermosetting resin is a silicone resin or a urethane resin.
  • the adhesive resin composition of the high heat conductive part contains a heat conductive filler and / or a conductive carbon compound.
  • the heat conductive filler includes at least one selected from the group consisting of metal oxides, metal nitrides, and metals.
  • the thermal conductivity of the high thermal conductive portion of the thermal conductive adhesive sheet is 0.5 (W / m ⁇ K) or more and the thermal conductivity of the low thermal conductive portion is less than 0.5 (W / m ⁇ K).
  • the heat conductive adhesive sheet of the present invention it is possible to improve the dimensional accuracy of the high heat conductive portion and the low heat conductive portion of the heat conductive adhesive sheet and to reduce the thermal conductivity of the low heat conductive portion. It is possible to provide a thermally conductive adhesive sheet that can be easily laminated without using a layer and can provide a sufficient temperature difference inside the electronic device, a method for producing the same, and an electronic device using the same. Moreover, since an adhesive layer is not required, the productivity of electronic devices is high, leading to low costs.
  • thermoelectric conversion device at the time of sticking the heat conductive adhesive sheet of this invention to the thermoelectric conversion module.
  • the heat conductive adhesive sheet and thermoelectric conversion module of this invention which show an example of the perspective view which decomposed
  • thermoelectric conversion module used for the Example of this invention. It is sectional drawing which shows an example of a structure of the conventional thermoelectric conversion device. It is sectional drawing which shows another example of a structure of the conventional thermoelectric conversion device. It is sectional drawing which shows another example of the structure of the conventional thermoelectric conversion device.
  • the heat conductive adhesive sheet of the present invention is a heat conductive adhesive sheet having a high heat conductive portion and a low heat conductive portion, the high heat conductive portion and the low heat conductive portion have adhesiveness, and a hollow filler is provided.
  • the low thermal conductivity portion contains 20 to 90% by volume in the total volume of the low thermal conductivity portion, and the high thermal conductivity portion and the low thermal conductivity portion independently constitute all the thicknesses of the thermal conductive adhesive sheet, or At least one is a heat conductive adhesive sheet which comprises a part of thickness of a heat conductive adhesive sheet.
  • FIG. 1 is a perspective view showing an example of the heat conductive adhesive sheet of the present invention.
  • the heat conductive adhesive sheet 1 is composed of high heat conductive portions 4a and 4b and low heat conductive portions 5a and 5b, which are alternately arranged.
  • the arrangement of the high thermal conductivity portion and the low thermal conductivity portion constituting the thermally conductive adhesive sheet (hereinafter sometimes referred to as “thickness configuration”) is not particularly limited as described below.
  • FIG. 2 shows various examples of cross-sectional views (including arrangement) of the heat conductive adhesive sheet of the present invention.
  • (A) of FIG. 2 is sectional drawing of FIG. 1, and the high heat conductive part 4 and the low heat conductive part 5 comprise all the thickness of the heat conductive adhesive sheet each independently. Further, in FIGS.
  • the low heat conductive portion 5 constitutes a part of the thickness of the heat conductive adhesive sheet.
  • the high heat conduction portion 4 constitutes a part of the thickness of the heat conductive adhesive sheet.
  • the configuration of the thickness of the heat conductive adhesive sheet can be appropriately selected in accordance with the specifications of the electronic device to be applied. For example, from the viewpoint of selectively dissipating heat in a specific direction, for example, it is preferable to select the thickness configuration shown in FIGS. 2A to 2E, and the thickness configuration shown in FIG. Is more preferable.
  • heat radiation can be efficiently controlled by increasing the volume of the high thermal conductivity portion and increasing the contact area with the device surface to be applied.
  • the low thermal conductive part of the present invention is formed from a resin composition containing a hollow filler and an adhesive resin described later.
  • the cure shrinkage rate of the low heat conduction part is suppressed and the difference from the cure shrinkage rate of the high heat conduction part is reduced, thereby reducing the composite cure shrinkage rate described later, resulting in high heat.
  • Deterioration of the dimensional accuracy of each pattern of the conduction part and the low heat conduction part can be suppressed.
  • the low thermal conductivity portion of the present invention refers to the one having lower thermal conductivity than the high thermal conductivity portion.
  • the hollow filler is not particularly limited, and known ones can be used.
  • inorganic hollows such as glass balloons, silica balloons, shirasu balloons, fly ash balloons, metal silicate balloons (hollow bodies).
  • the filler include organic resin-based hollow fillers that are balloons (hollow bodies) such as acrylonitrile, vinylidene chloride, phenolic resin, epoxy resin, and urea resin.
  • a hollow filler can be used individually by 1 type or in combination of 2 or more types. Among these, the thermal conductivity of the substance itself is relatively low among metal oxides, and from the viewpoint of volume resistivity and cost, glass hollow fillers or silica hollow fillers that are inorganic hollow fillers are preferred.
  • the glass hollow filler for example, Glass Bubbles (soda lime borosilicate glass) manufactured by Sumitomo 3M Co., Ltd.
  • silica hollow filler for example, Silax (registered by Nippon Steel Mining Co., Ltd.) Trademark) and the like.
  • the “hollow filler” has an outer shell having a filler as a constituent material, and the inside is a hollow structure (the inside may be filled with a gas such as an inert gas other than air,
  • the hollow structure is not particularly limited.
  • the hollow structure may be a sphere or an ellipsoid, and there are a plurality of hollow structures. May be.
  • the shape of the hollow filler is not particularly limited, but when pasted on the applied electronic device, element, etc., the electrical characteristics of the electronic device, element, etc. are not impaired by contact or mechanical damage. Any shape may be used, and for example, any of a plate shape (including a scale shape), a spherical shape, a needle shape, a rod shape, and a fiber shape may be used.
  • the size of the hollow filler is, for example, preferably from 0.1 to 200 ⁇ m, more preferably from 1 to 100 ⁇ m, from the viewpoint of uniformly dispersing the hollow filler in the thickness direction of the low heat conduction part and reducing the thermal conductivity. 10 to 80 ⁇ m is more preferable, and 20 to 50 ⁇ m is particularly preferable. If the average particle diameter of the hollow filler is within this range, the particles are hardly aggregated and can be uniformly dispersed. Furthermore, the packing density in the low heat conduction part becomes sufficient, and the low heat conduction part does not become brittle at the substance interface.
  • the average particle diameter can be measured by, for example, a Coulter counter method.
  • the content of the hollow filler is appropriately adjusted according to the particle shape, and is 20 to 90% by volume, preferably 40 to 80% by volume, and more preferably 50 to 70% by volume in the adhesive resin composition.
  • the content of the hollow filler is less than 20% by volume, curing shrinkage becomes large, and the pattern dimensional accuracy of the high heat conduction part and the low heat conduction part decreases.
  • the content of the hollow filler exceeds 90% by volume, the mechanical strength of the low heat conducting part cannot be maintained.
  • the content of the hollow filler is in this range, curing shrinkage is effectively suppressed, heat dissipation characteristics, folding resistance, and bending resistance are excellent, and the mechanical strength of the low heat conducting portion is maintained.
  • the true density of the hollow filler is preferably 0.1 to 0.6 g / cm 3 , more preferably 0.2 to 0.5 g / cm 3, and still more preferably 0.3 to 0.4 g / cm 3 . If the true density of the hollow filler is within this range, the heat insulating properties and pressure resistance are excellent, the hollow filler is not crushed when the low thermal conductive portion is formed, and the low thermal conductivity of the low thermal conductive portion is not impaired.
  • the “true density” is a density measured by a pycnometer method (a gas phase method based on Archimedes' principle). For example, it can be measured using a pycnometer (gas phase substitution true density meter, for example, AccuPycII 1340 manufactured by Micromeritics).
  • the adhesive resin used in the present invention is not particularly limited, but any resin can be appropriately selected from those used in the field of electronic components, for example, thermosetting resin, energy beam curable resin, etc. Is mentioned.
  • thermosetting resin examples include epoxy resin, melamine resin, urea resin, phenol resin, silicone resin, urethane resin, polyimide resin, benzoxazine resin, thermosetting acrylic resin, and unsaturated polyester resin.
  • urethane resins and silicone resins are preferable from the viewpoint of excellent heat resistance and high adhesive strength.
  • Urethane resins include a reaction product of a hydroxyl group-containing compound and a polyisocyanate compound, for example, a polyurethane obtained by a reaction of a short-chain glycol or a short-chain ether with an isocyanate compound as a hard segment, and a long-chain glycol or a long as a soft segment.
  • a reaction product (cured product) of a urethane prepolymer and a polyisocyanate compound may be used.
  • the silicone resin a thermosetting addition reaction type silicone resin can be used.
  • the addition reaction type silicone resin include at least one selected from polyorganosiloxanes having an alkenyl group as a functional group in the molecule.
  • Preferred examples of the polyorganosiloxane having an alkenyl group as a functional group in the molecule include polydimethylsiloxane having a vinyl group as a functional group, polydimethylsiloxane having a hexenyl group as a functional group, and a mixture thereof. .
  • thermosetting resin When the thermosetting resin is used, it is preferable to use a curing agent, a curing accelerator, a curing retarder, a curing catalyst, or the like as an auxiliary agent.
  • the curing agent include compounds having two or more functional groups capable of reacting with the functional groups of the thermosetting resin component in one molecule.
  • the curing agent for the epoxy resin include a phenol curing agent, an alcohol curing agent, an amine curing agent, and an aluminum chelate curing agent.
  • the curing agent for the silicone resin include a hydrosilyl curing agent.
  • Curing accelerators include, for example, tertiary amines such as triethylenediamine and benzyldimethylamine; imidazoles such as 2-methylimidazole and 2-phenylimidazole; organic phosphines such as tribrituphosphine and diphenylphosphine; tetraphenyl Examples thereof include tetraphenylboron salts such as phosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
  • the curing retarder include hydrosilylation reaction control agents.
  • the curing catalyst include a platinum catalyst, a palladium catalyst, and a rhodium catalyst.
  • the content of the auxiliary agent varies depending on the type of thermosetting resin, but is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 100 parts by weight of the thermosetting resin. 30 to 70 parts by mass.
  • the energy beam curable resin examples include a compound having one or more polymerizable unsaturated bonds such as a compound having an acrylate functional group.
  • the compound having one polymerizable unsaturated bond examples include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like.
  • Examples of the compound having two or more polymerizable unsaturated bonds include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate.
  • Polyfunctional compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and modified products thereof, and , Reaction products of these polyfunctional compounds with (meth) acrylates and the like (for example, poly (meth) acrylate esters of polyhydric alcohols), and the like.
  • (meth) acrylate means methacrylate and acrylate.
  • polyester resins having a polymerizable unsaturated bond polyether resins, acrylic resins, epoxy resins, urethane resins, silicone resins, polybutadiene resins, etc. are also used as the energy ray curable resins. be able to.
  • the photoinitiator used for this invention is contained in the adhesive resin composition containing the said energy beam curable resin, and can cure the said energy beam curable resin under an ultraviolet-ray.
  • photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethyl Tylamine benzoate can be used.
  • a photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
  • the blending amount is usually selected in the range of 0.2 to 10 parts by mass with respect to 100 parts by mass of the energy beam curable resin.
  • the mass average molecular weight of the adhesive resin used in the present invention is usually several hundred to several million.
  • the adhesive resin composition can be used within an appropriate range as needed, for example, a crosslinking agent, a filler, a plasticizer, an anti-aging agent, an antioxidant, an ultraviolet absorber, a colorant such as a pigment or a dye, and an adhesive.
  • An additive such as an imparting agent, an antistatic agent or a coupling agent, or a non-adhesive resin may be contained.
  • non-adhesive resins examples include polyester resins, urethane resins, silicone resins, rubber polymers, polyolefin resins, styrene resins, amide resins, cyclic olefin resins, vinyl chloride resins, polyimide resins, polycarbonate resins, and polysulfone resins. It is done.
  • the shape of the high heat conduction part is not particularly limited, as is the case with the low heat conduction part, and can be appropriately changed according to the specifications of an electronic device or the like described later.
  • the high thermal conductivity part of the present invention refers to the one having higher thermal conductivity than the low thermal conductivity part.
  • the high heat conduction part is not particularly limited as long as it is formed of an adhesive resin composition and has a higher thermal conductivity than the low heat conduction part.
  • the adhesive resin examples include the same resins such as the thermosetting resin and the energy curable resin used in the low thermal conductive portion described above. Usually, the same resin as that of the low heat conducting part is used from the viewpoint of mechanical properties, adhesion and the like.
  • the high heat conduction part is preferably formed from a resin composition containing the adhesive resin, a heat conductive filler, and / or a conductive carbon compound in order to adjust to a desired heat conductivity described later.
  • the thermally conductive filler and the conductive carbon compound may be referred to as “thermal conductivity adjusting substance”.
  • the heat conductive filler is not particularly limited, but may be selected from metal oxides such as silica, alumina and magnesium oxide, metal nitrides such as silicon nitride, aluminum nitride, magnesium nitride and boron nitride, and metals such as copper and aluminum.
  • metal oxides such as silica, alumina and magnesium oxide
  • metal nitrides such as silicon nitride, aluminum nitride, magnesium nitride and boron nitride
  • metals such as copper and aluminum.
  • At least one selected, and the conductive carbon compound is preferably at least one selected from carbon black, carbon nanotube (CNT), graphene, carbon nanofiber, and the like.
  • heat from metal oxides such as silica, alumina, magnesium oxide, metal nitrides such as silicon nitride, aluminum nitride, magnesium nitride, boron nitride, etc. from the point of being easily in the volume resistivity range described later.
  • Conductive fillers are preferred.
  • a metal oxide and a metal nitride are included.
  • the mass ratio of the metal oxide and the metal nitride is preferably 10:90 to 90:10, and 20:80 to 80:20. More preferred is 50:50 to 75:25.
  • the shape of the material for adjusting the thermal conductivity is not particularly limited, but electrical properties of the electronic device, element, etc. due to contact or mechanical damage when applied to the applied electronic device, element, etc.
  • any of a plate shape (including a scale shape), a spherical shape, a needle shape, a rod shape, and a fiber shape may be used.
  • the above-mentioned “hollow filler” is not included in the heat conductive filler used in the high heat conductive portion.
  • the size of the thermal conductivity adjusting material is, for example, an average particle size of 0.1 to 200 ⁇ m. It is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, particularly preferably 10 to 30 ⁇ m.
  • the average particle diameter can be measured by, for example, a Coulter counter method. If the average particle diameter of the thermal conductivity adjusting substance is within this range, the thermal conductivity within each substance is not reduced, and as a result, the thermal conductivity of the high thermal conductivity portion is improved. In addition, the particles are less likely to aggregate and can be uniformly dispersed. Further, the packing density in the high heat conduction part is sufficient, and the high heat conduction part does not become brittle at the substance interface.
  • the content of the thermal conductivity adjusting substance is appropriately adjusted according to the desired thermal conductivity, and is preferably 40 to 99% by mass, more preferably 50 to 95% by mass in the adhesive resin composition, and 50 to 80%. Mass% is particularly preferred. If the content of the material for adjusting the thermal conductivity is within this range, the heat dissipation characteristics, folding resistance, and bending resistance are excellent, and the strength of the high thermal conductivity portion is maintained.
  • the high thermal conductivity portion may further contain the same type of additive within an appropriate range as necessary, similarly to the low thermal conductivity portion.
  • the thickness of each layer of the high heat conduction part and the low heat conduction part is preferably 1 to 200 ⁇ m, and more preferably 3 to 100 ⁇ m. Within this range, heat can be selectively radiated in a specific direction. Moreover, the thickness of each layer of a high heat conduction part and a low heat conduction part may be the same, or may differ.
  • the width of each layer of the high heat conduction part and the low heat conduction part is appropriately adjusted according to the specification of the applied electronic device, but is usually 0.01 to 3 mm, preferably 0.1 to 2 mm, and more preferably 0. 5 to 1.5 mm. Within this range, heat can be selectively radiated in a specific direction. Moreover, the width of each layer of the high heat conduction part and the low heat conduction part may be the same or different.
  • the heat conductivity of the high heat conduction part should be sufficiently higher than that of the low heat conduction part, and the heat conductivity is preferably 0.5 (W / m ⁇ K) or more, and 1.0 (W / m ⁇ K) or more. Is more preferable, and 1.3 (W / m ⁇ K) or more is more preferable.
  • the heat conductivity of a high heat conductive part Usually 2000 (W / m * K) or less is preferable and 500 (W / m * K) or less is more preferable.
  • the thermal conductivity of the low thermal conductivity part is preferably less than 0.5 (W / m ⁇ K), more preferably 0.3 (W / m ⁇ K) or less, and 0.25 (W / m ⁇ K) or less. Further preferred. If the conductivity of the high heat conduction part and the low heat conduction part is in the above range, heat can be selectively radiated in a specific direction.
  • the composite curing shrinkage ratio of the adhesive resin composition of each of the high heat conduction part and the low heat conduction part is preferably 2% or less, and more preferably 1% or less. If the composite curing shrinkage rate is within this range, the pattern dimensional accuracy of the high heat conduction part and the low heat conduction part is improved, heat is selectively radiated in a specific direction, and a sufficient temperature difference is present inside the electronic device or the like. Can be granted.
  • the above-mentioned “composite curing shrinkage rate” is formed from an adhesive resin composition that constitutes the high heat conduction part, for example, an adhesive resin composition that constitutes the stripe pattern and the low heat conduction part.
  • Composite cure shrinkage (%) [(full width in stripe pattern pitch direction before curing ⁇ full width in stripe pattern pitch direction after cure) / full width in stripe pattern pitch direction before cure] ⁇ 100
  • the width in the pitch direction and the low heat conduction part of the high heat conduction part stripe pattern formed from the adhesive resin composition for forming a high heat conduction part A digital multimeter (manufactured by Nippon Koki Co., Ltd.) is used for the total width (that is, the total width in the pitch direction of the stripe pattern) of the low thermal conduction part stripe pattern formed from the forming adhesive resin composition before and after curing.
  • Stripe pattern (adhesive resin composition) group 100 mm ⁇ 100 mm, thickness 100 ⁇ m High heat conduction part: stripe width 1 mm, length 100 mm, thickness 100 ⁇ m Low heat conduction part: stripe width 1 mm, length 100 mm, thickness 100 ⁇ m ⁇
  • High heat conduction parts (stripe) and low heat conduction parts (stripe) in the pitch direction (however, the space between stripes is zero)
  • the thickness of the heat conductive adhesive sheet is different (the thicknesses of the high heat conduction portion and the low heat conduction portion in FIGS.
  • the storage elastic modulus at 150 ° C. after curing of the high heat conduction part is preferably 0.1 MPa or more, more preferably 0.15 MPa or more, and further preferably 1 MPa or more. Further, the storage elastic modulus at 150 ° C. after curing of the low heat conducting part is preferably 0.1 MPa or more, more preferably 0.15 MPa or more, and further preferably 1 MPa or more.
  • the heat conductive adhesive sheet is suppressed from being excessively deformed, and can stably dissipate heat. it can.
  • the storage modulus at 0 ° C. can be adjusted.
  • the storage elastic modulus at 150 ° C. is increased to 150 ° C. at an initial temperature of 15 ° C. and a temperature increase rate of 3 ° C./min using a dynamic elastic modulus measuring device (TA Instruments, model name “DMAQ800”). It is a value measured at a frequency of 11 Hz by heating.
  • the volume resistivity of the high heat conduction part and the low heat conduction part is preferably 1 ⁇ 10 10 ⁇ ⁇ cm or more, and more preferably 1.0 ⁇ 10 13 ⁇ ⁇ cm or more.
  • the volume resistivity is a value measured with a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., MCP-HT450) after leaving the thermally conductive adhesive sheet in an environment of 23 ° C. and 50% RH for one day.
  • the level difference between the high thermal conductivity portion and the low thermal conductivity portion is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably substantially absent.
  • At least one of the high heat conduction portion and the low heat conduction portion constitutes a part of the thickness of the base material.
  • the step between the high heat conduction portion and the low heat conduction portion is It is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably substantially absent.
  • the thickness of the base material is defined as the thickness composed of the high heat conduction portion and the low heat conduction portion.
  • the step difference between the high heat conduction portion and the low heat conduction portion is preferably 10 to 90% with respect to the thickness.
  • the volume ratio of the high heat conductive portion to the low heat conductive portion is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and 30 : 70 to 70:30 is more preferable.
  • the heat conductive adhesive sheet may have a release sheet on one side or both sides.
  • the release sheet include papers such as glassine paper, coated paper, and laminated paper, and various plastic films coated with a release agent such as silicone resin and fluororesin.
  • the thickness of the release sheet is not particularly limited, but is usually 10 to 200 ⁇ m.
  • As the support substrate used for the release sheet used in the present invention it is preferable to use a plastic film.
  • the electronic device using the heat conductive adhesive sheet of the present invention is not particularly limited, and examples thereof include semiconductor devices such as thermoelectric conversion devices, photoelectric conversion devices, and large-scale integrated circuits from the viewpoint of heat control such as heat dissipation.
  • the heat conductive adhesive sheet can be selectively dissipated in a specific direction by sticking to the thermoelectric conversion module of the thermoelectric conversion device, leading to further improvement in thermoelectric performance.
  • the heat conductive adhesive sheet may be laminated
  • a thermoelectric conversion device is used as the electronic device will be described as an example.
  • thermoelectric conversion device is an electronic device in which electric power can be easily obtained by applying a temperature difference to the inside of a thermoelectric conversion element that performs mutual energy conversion between heat and electricity.
  • FIG. 3 is a cross-sectional view showing an example of a thermoelectric conversion device when the heat conductive adhesive sheet of the present invention having the configuration shown in FIG. 2A is attached to a thermoelectric conversion module.
  • the thermoelectric conversion device 10 shown in FIG. 3 includes a thin P-type thermoelectric element 11 made of P-type material and a thin-film N-type thermoelectric element 12 made of N-type material on a support (not shown).
  • thermoelectric conversion module 16 having a thermoelectric conversion element and further provided with an electrode 13, a heat conductive adhesive sheet 1A attached to the first surface 17 of the thermoelectric conversion module 16, and the first surface 17 It is comprised from the heat conductive adhesive sheet 1B affixed on the 2nd surface 18 of the other side.
  • heat conductive adhesive sheets have high heat conductive part 14a, 14b and low heat conductive part 15a, 15b, 15c, and this high heat conductive part 14a, 14b and this low heat conductive part 15a, 15b, 15c have adhesiveness. And they constitute the outer surface of the thermally conductive adhesive sheet.
  • the heat conductive adhesive sheet 1B has high heat conduction portions 14'a, 14'b, 14'c and low heat conduction portions 15'a, 15'b, and the high heat conduction portions 14'a, 14'c. b and 14'c and the low thermal conductive portions 15'a and 15'b have adhesiveness, and they constitute the outer surface of the thermal conductive adhesive sheet.
  • FIG. 4 shows an example of a perspective view in which the heat conductive adhesive sheet and the thermoelectric conversion module of the present invention are disassembled for each component.
  • 4A is a perspective view of the heat conductive adhesive sheet 1A directly provided on the thermoelectric elements 11 and 12 on the surface side of the support 19 of the thermoelectric conversion module 16
  • FIG. 4B is a perspective view of the thermoelectric conversion module 16.
  • (c) is a perspective view of the heat conductive adhesive sheet 1B provided in the back surface side of the support body 19 of the thermoelectric conversion module 16.
  • FIG. By taking the above configuration, heat can be efficiently diffused from the heat conductive adhesive sheet 1A and the heat conductive adhesive sheet 1B.
  • the high heat conductive portions 14a and 14b of the heat conductive adhesive sheet 1A and the high heat conductive portions 14'a, 14'b and 14'c of the heat conductive adhesive sheet 1B are stacked so as not to face each other. By doing so, heat can be selectively radiated in a specific direction. Thereby, a temperature difference can be efficiently given to a thermoelectric conversion module, and a thermoelectric conversion device with high power generation efficiency is obtained.
  • thermoelectric conversion module 16 used for this invention is comprised from the P-type thermoelectric element 11, the N-type thermoelectric element 12, and the electrode 13, as FIG.4 (b) shows, for example.
  • the P-type thermoelectric element 11 and the N-type thermoelectric element 12 are formed in a thin film shape so as to be connected in series, and are joined and electrically connected via electrodes 13 at their respective ends.
  • the P-type thermoelectric element 11 and the N-type thermoelectric element 12 in the thermoelectric conversion module 16 are “electrode 13, P-type thermoelectric element 11, electrode 13, N-type thermoelectric element 12, electrode 13,.
  • thermoelectric conversion module may be formed directly on the high heat conduction portion and the low heat conduction portion, or may be formed through other layers, but it can efficiently impart a temperature difference to the thermoelectric element. From the point, it is preferable that the thermoelectric conversion module is directly formed on the high heat conduction part and the low heat conduction part.
  • thermoelectric element is not particularly limited, but in the temperature range of the heat source converted into electric energy by the thermoelectric conversion module, the absolute value of the Seebeck coefficient is large, the thermal conductivity is low, and the so-called thermoelectric performance is high. It is preferable to use a material with a high index.
  • the material constituting the P-type thermoelectric element and the N-type thermoelectric element is not particularly limited as long as it has thermoelectric conversion characteristics, but bismuth-tellurium-based thermoelectric semiconductor materials such as bismuth telluride and Bi 2 Te 3 , GeTe, Telluride-based thermoelectric semiconductor materials such as PbTe, antimony-tellurium-based thermoelectric semiconductor materials, zinc-antimony-based thermoelectric semiconductor materials such as ZnSb, Zn 3 Sb 2 , Zn 4 Sb 3 , silicon-germanium-based thermoelectric semiconductor materials such as SiGe, Bi Bismuth selenide thermoelectric semiconductor materials such as 2 Se 3 , silicide thermoelectric semiconductor materials such as ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , Mg 2 Si, oxide thermoelectric semiconductor materials, FeVAl, FeVAlSi, FeVTiAl, etc.
  • bismuth-tellurium-based thermoelectric semiconductor materials such as bismuth telluride and Bi 2 Te 3
  • the thicknesses of the P-type thermoelectric element 11 and the N-type thermoelectric element 12 are preferably 0.1 to 100 ⁇ m, and more preferably 1 to 50 ⁇ m. Note that the thicknesses of the P-type thermoelectric element 11 and the N-type thermoelectric element 12 are not particularly limited, and may be the same or different.
  • the manufacturing method of the heat conductive adhesive sheet of the present invention comprises a high heat conductive portion and a low heat conductive portion, and the high heat conductive portion and the low heat conductive portion independently constitute all the thicknesses of the heat conductive adhesive sheet. Or a method for producing a heat conductive adhesive sheet in which one of them constitutes a part of the thickness of the heat conductive adhesive sheet, wherein the high heat conductive part is formed from the adhesive resin composition on the release sheet And a step of forming a low thermal conductive portion formed from the adhesive resin composition.
  • the high heat conduction part is formed on the release sheet, or on the release sheet and on the low heat conduction part using the adhesive resin composition containing an adhesive resin and a heat conductive filler and / or a conductive carbon compound.
  • the method for applying the adhesive resin composition is not particularly limited, and may be formed by a known method such as a stencil printing method, a dispenser, a screen printing method, a roll coating method, or a slot die.
  • the curing conditions when a thermosetting adhesive resin is used are appropriately adjusted depending on the composition used, but are preferably 80 ° C.
  • examples of the energy radiation include an electron beam, an X-ray, radiation, visible light and the like in addition to ultraviolet rays.
  • ultraviolet rays are preferably used, and as a light source, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • the amount of light is usually 100 to 1500 mJ / cm 2 .
  • an electron beam accelerator or the like When an electron beam is used, an electron beam accelerator or the like is used, and the irradiation amount is usually 150 to 350 kV. In addition, when using an ultraviolet-ray, it is necessary to add the photoinitiator mentioned above to the adhesive resin composition. Moreover, when using an electron beam, a cured film can be obtained, without adding a photoinitiator.
  • the low heat conduction part is formed on the release sheet, or on the release sheet and on the high heat conduction part, similarly to the formation of the high heat conduction part, using the adhesive resin composition containing an adhesive resin and a hollow filler.
  • the application method of the adhesive resin composition is not particularly limited, and it is formed by a known method such as a stencil printing method, a dispenser, a screen printing method, a roll coating method, a slot die, etc., as in the case of the high heat conduction part. do it.
  • the curing method is the same as the curing method for the high thermal conductivity portion.
  • the order in which the high heat conduction part and the low heat conduction part are formed is not particularly limited. What is necessary is just to select suitably according to the specification of an electronic device.
  • heat conduction bonding with high dimensional accuracy in which heat is released or heat flow can be controlled in a specific direction and curing shrinkage is suppressed in an electronic device or the like by a simple method.
  • Sheets can be manufactured.
  • Composite cure shrinkage rate is a stripe pattern formed from an adhesive resin composition for forming a high heat conduction part and an adhesive resin for forming a low heat conduction part with a release sheet.
  • Stripe pattern group 100 mm ⁇ 100 mm, thickness 100 ⁇ m; however, the configuration of the thickness of the heat conductive adhesive sheet is different, and the stripe pattern is a high heat conduction part or a low heat conduction part.
  • the digital multimeter measures the dimensional change before and after curing (curing conditions: depending on the resin composition used, but performed under optimum curing conditions) of the entire width in the pitch direction of (including the case where only at least one of these is included) (NRM-S3-XY type, manufactured by Nippon Koki Co., Ltd.) and calculated from the following formula.
  • Composite cure shrinkage (%) [(full width in stripe pattern pitch direction before curing ⁇ full width in stripe pattern pitch direction after cure) / full width in stripe pattern pitch direction before cure] ⁇ 100
  • the specification of the stripe pattern is as described above, and the dimension measurement after curing is performed without the release sheet in order to prevent the release sheet from suppressing the shrinkage of the cured product, that is, the stress relaxation after curing is released. It performed with respect to the hardened
  • thermocouple chromel alumel
  • thermoelectric conversion module As shown in part of FIG. 6, on a support 26, a P-type thermoelectric element 21 (P-type bismuth-tellurium-based thermoelectric semiconductor material) and an N-type thermoelectric element 22 (N-type bismuth-tellurium-based thermoelectric semiconductor material). Are arranged so as to have the same size (width 1.7 mm ⁇ length 100 mm, thickness 0.5 mm), and both the thermoelectric elements and the copper electrodes (copper electrode 23a: width 0 .0) between the thermoelectric elements.
  • P-type thermoelectric element 21 P-type bismuth-tellurium-based thermoelectric semiconductor material
  • N-type thermoelectric element 22 N-type bismuth-tellurium-based thermoelectric semiconductor material
  • thermoelectric conversion module 27 15 mm ⁇ length 100 mm, thickness 0.5 mm; copper electrode 23b: width 0.3 mm ⁇ length 100 mm, thickness 0.5 mm; copper electrode 23c: width 0.15 mm ⁇ length 100 mm, thickness 0.5 mm) A thermoelectric conversion module 27 was produced.
  • Example 1 (1) Production of Thermally Conductive Adhesive Sheet Silicone Resin A (Asahi Kasei Wacker, “SilGel612-A”) 19.8 parts by mass, Silicone Resin B (Asahi Kasei Wacker, “SilGel612-B”) 19.8 parts by mass Parts, 0.4 parts by mass of a retarder (Asahi Kasei Wacker, “PT88”), 40 parts by mass of alumina (manufactured by Showa Denko, “Aruna Beads CB-A20S”, average particle diameter 20 ⁇ m) as a thermally conductive filler, Add 20 parts by weight of boron nitride (Showa Denko Co., Ltd., “ShowNu UHP-2”, average particle size: 12 ⁇ m), and mix and disperse using a rotating / revolving mixer (THINKY, “ARE-250”).
  • a retarder Asahi Kasei Wacker, “PT88”
  • silicone resin A (Asahi Kasei Wacker, “SilGel612-A”) 31.7 parts by mass
  • silicone resin B (Asahi Kasei Wacker, “SilGel612-B”) 31.7 parts by mass
  • curing retarder (Asahi Kasei Wacker) 0.6 parts by mass
  • PT88 manufactured by the company
  • glass Bubbles S38 average particle size 40 ⁇ m, true density 0.38 g / cm 3
  • the adhesive resin composition for forming the high thermal conductive portion was applied to the surface of the release sheet (“PET50FD” manufactured by Lintec Corporation) on which the release treatment was performed, and dispenser (“ML-808FXcom-CE” manufactured by Musashi Engineering Co., Ltd.).
  • ML-808FXcom-CE manufactured by Musashi Engineering Co., Ltd.
  • a highly heat conductive portion 24 (see FIG. 6) having a stripe pattern (width 1 mm ⁇ length 100 mm, thickness 50 ⁇ m, pattern center distance 2 mm).
  • an adhesive resin composition for forming a low heat conduction part is applied, dried at 150 ° C. for 5 minutes, and then heated at 150 ° C. for 30 minutes to cure the heat conductive adhesive sheet.
  • a heat conductive adhesive sheet was obtained in which the low heat conductive portion 25 (see FIG. 6) having the same thickness as the high heat conductive portion was formed between the stripe patterns of the high heat conductive portion. In addition, it confirmed that the low heat conductive part was not formed on the high heat conductive part.
  • thermoelectric conversion device Prepare two sheets of the obtained heat conductive adhesive sheet, and, as shown in FIG. 6, the heat conductive adhesive sheet and the surface on the side where the thermoelectric element of the thermoelectric conversion module 27 is formed A thermoelectric conversion device was prepared by laminating each on the surface on the support side and laminating a heat conductive adhesive sheet on both sides.
  • the storage elastic modulus at 150 ° C. after the curing of the high heat conducting portion 24 was 2.3 MPa
  • the storage elastic modulus at 150 ° C. after the curing of the low heat conducting portion 25 was 1.6 MPa.
  • the volume resistivity of the high thermal conductivity portion 24 was 7.2 ⁇ 10 14 ⁇ ⁇ cm
  • the volume resistivity of the low thermal conductivity portion 25 was 2.4 ⁇ 10 15 ⁇ ⁇ cm.
  • Example 2 42.6 parts by mass of an adhesive resin composition for forming a low thermal conductive part, silicone resin A (Asahi Kasei Wacker, “SilGel612-A”), silicone resin B (Asahi Kasei Wacker, “SilGel612-B”) 6 parts by weight, 0.8 parts by weight of a retarder (Asahi Kasei Wacker, “PT88”), hollow filler, glass hollow filler (Sumitomo 3M, “Glass Bubbles S38”, average particle diameter 40 ⁇ m, true density 0.38 g / cm 3 )
  • a heat conductive adhesive sheet and a thermoelectric conversion device were prepared in the same manner as in Example 1 except that 14 parts by mass (the total volume of the low heat conductive part was 30% by volume of the glass hollow filler).
  • the storage elastic modulus at 150 ° C. after curing of the high thermal conductivity portion was 2.3 MPa
  • the storage elastic modulus at 150 ° C. after curing of the low thermal conductivity portion was 0.2 MPa.
  • the volume resistivity of the high heat conduction part was 7.2 ⁇ 10 14 ⁇ ⁇ cm
  • the volume resistivity of the low heat conduction part was 2.4 ⁇ 10 15 ⁇ ⁇ cm.
  • Example 3 Using the adhesive resin composition for forming a high thermal conductive part used in Example 1, a striped pattern (width 1 mm ⁇ length 100 mm, thickness) was formed on the release-treated surface of the release sheet in the same manner as in Example 1. A high heat conduction portion having a thickness of 50 ⁇ m and a distance between pattern centers of 2 mm was formed. Next, the adhesive resin composition for forming a low thermal conductive part used in Example 1 was applied thereon, dried at 150 ° C. for 5 minutes, and then heated at 150 ° C. for 30 minutes to cure the thermally conductive adhesive sheet. A low heat conductive part having a thickness of 75 ⁇ m was formed to produce a heat conductive adhesive sheet.
  • a low heat conduction part is formed between the stripe-like patterns of the high heat conduction part and on the high heat conduction part, and a low heat conduction part having a thickness of 25 ⁇ m is formed on the high heat conduction layer part.
  • Two sheets of the obtained heat conductive adhesive sheet were prepared, and in the same manner as in Example 1, the surface of the thermoelectric conversion module 27 on the side where the thermoelectric elements were formed and the surface on the support side, the lower surface of FIG. Like the side, the side surface comprised only by the low heat conductive part was laminated
  • Example 4 Two heat conductive adhesive sheets obtained in Example 3 were prepared, and the heat conductive adhesive sheet was placed on the surface on the side where the thermoelectric elements of the thermoelectric conversion module 27 were formed and the surface on the support side as shown in FIG. As in the upper surface side, a surface composed of a high heat conduction part and a low heat conduction part was laminated to each other to be laminated, and a thermoelectric conversion device in which a heat conductive adhesive sheet was laminated on both surfaces was produced.
  • Example 5 Example 1 except that hollow nanosilica (“SILINAX” (registered trademark), average particle diameter 105 nm, true density 0.57 g / cm 3 ) manufactured by Nippon Steel Mining Co., Ltd.) is used as the hollow filler.
  • SILINAX registered trademark
  • a thermoelectric conversion device was prepared in the same manner as described above.
  • Example 1 A heat conductive adhesive sheet and a thermoelectric conversion device using the same were produced in the same manner as in Example 1 except that the glass hollow filler was not added to the low heat conductive part.
  • the storage elastic modulus at 150 ° C. after curing of the high thermal conductivity portion was 2.3 MPa
  • the storage elastic modulus at 150 ° C. after curing of the low thermal conductivity portion was 0.2 MPa.
  • the volume resistivity of the high heat conduction part was 7.2 ⁇ 10 14 ⁇ ⁇ cm
  • the volume resistivity of the low heat conduction part was 2.6 ⁇ 10 15 ⁇ ⁇ cm.
  • thermoelectric conversion device An adhesive-processed PGS graphite sheet (manufactured by Panasonic Corporation, product number: EYGA09201M, PGS graphite sheet thickness: 10 ⁇ m, adhesive thickness 10 ⁇ m, thermal conductivity: 1950 (W / m ⁇ K)) was used as the heat conductive adhesive sheet.
  • Two heat conductive adhesive sheets are prepared, and the heat conductive adhesive sheets are laminated on the surface on which the thermoelectric element of the thermoelectric conversion module 27 is formed and the surface on the support side, respectively, and the heat conductive adhesive sheets are laminated on both sides.
  • a thermoelectric conversion device was manufactured.
  • thermoelectric conversion module 27 (Comparative Example 3) The temperature difference was measured without attaching the heat conductive adhesive sheet to the adherend. Moreover, the electronic device evaluation was performed without laminating the heat conductive adhesive sheet on the thermoelectric conversion module 27.
  • Table 1 shows the evaluation results of the composite curing shrinkage rate, thermal conductivity, temperature difference and / or electronic (thermoelectric conversion) device such as the thermally conductive adhesive sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 3. .
  • the result of the evaluation of the electronic device of Comparative Example 1 was 0 because the misalignment at the time of bonding between the heat conductive adhesive sheet and the thermoelectric conversion element was large (derived from composite curing shrinkage), which is appropriate for the thermoelectric conversion element. It is considered that a temperature difference could not be imparted to.
  • the heat conductive adhesive sheet of the present invention can be applied with high dimensional accuracy to a thermoelectric element or the like, particularly when applied to a thermoelectric conversion module of a thermoelectric conversion device which is one of electronic devices, and has a high thermal conductivity with a high heat conductive portion. Since the difference can be made larger, a temperature difference can be efficiently imparted in the thickness direction of the thermoelectric element. For this reason, power generation with high power generation efficiency is possible, and the number of thermoelectric conversion modules installed can be reduced compared to the conventional type, leading to downsizing and cost reduction.
  • the heat conductive adhesive sheet of the present invention can be used as a flexible thermoelectric conversion device without being restricted in installation place, such as being installed on a waste heat source or a heat radiation source having a non-planar surface. .
  • thermoelectric conversion device 11 P-type thermoelectric Element 12: N-type thermoelectric element 13: Electrode (copper) 14a, 14b: High heat conduction parts 14'a, 14'b, 14'c: High heat conduction parts 15a, 15b, 15c: Low heat conduction parts 15'a, 15'b: Low heat conduction parts 16: Thermoelectric conversion module 17: 16 first surface 18: 16 second surface 19: support 20: thermoelectric conversion device 21: P-type thermoelectric element 22: N-type thermoelectric elements 23a, 23b, 23c: electrodes (copper) 24: High heat conduction part 25: Low heat conduction part 26: Support 27: Thermoelectric conversion module 28: Lower surface 29: 27 Upper surface 41: P-type thermoelectric element 42: N-type thermoelectric element 43: Electrode (co

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Abstract

L'invention concerne une feuille adhésive thermoconductrice qui permet une amélioration de la précision dimensionnelle d'une partie à forte conductivité thermique et d'une partie à faible conductivité thermique de la feuille adhésive thermoconductrice, une réduction de la conductivité thermique de la partie à faible conductivité thermique, un placage facile sur un dispositif électronique sans qu'il soit nécessaire d'interposer de couche adhésive et la génération d'une différence de température suffisante à l'intérieur du dispositif électronique ; un procédé de fabrication de la feuille adhésive thermoconductrice ; et un dispositif électronique utilisant la feuille adhésive thermoconductrice. La feuille adhésive thermoconductrice comprend la partie à forte conductivité thermique et la partie à faible conductivité thermique. La partie à forte conductivité thermique et la partie à faible conductivité thermique sont adhésives. La partie à faible conductivité thermique contient de 20 à 90 % en volume d'une charge creuse par rapport au volume total de la partie à faible conductivité thermique. La partie à forte conductivité thermique ou la partie à faible conductivité thermique constituent, indépendamment l'une de l'autre, l'épaisseur totale de la feuille adhésive thermoconductrice, ou au moins l'une des deux constitue une partie de l'épaisseur de la feuille adhésive thermoconductrice.
PCT/JP2015/073289 2014-12-26 2015-08-20 Feuille adhésive thermoconductrice, son procédé de fabrication et dispositif électronique l'utilisant WO2016103783A1 (fr)

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JP6336688B1 (ja) * 2017-02-13 2018-06-06 新電元工業株式会社 電子モジュール
JP2020063414A (ja) * 2018-08-20 2020-04-23 テーザ・ソシエタス・ヨーロピア 長尺材料、特にケーブルハーネスをジャケッティングするための接着テープおよびジャケッティング方法
KR20200055189A (ko) * 2018-11-12 2020-05-21 주식회사 대현에스티 방열 점착제의 제조방법 및 이를 포함하는 방열 테이프
CN112313794A (zh) * 2018-06-27 2021-02-02 京瓷株式会社 电子元件搭载用基板、电子装置以及电子模块

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