WO2018078436A1

WO2018078436A1 - Three-dimensionally shaped thermally conductive molded body, and manufacturing method thereof

Info

Publication number: WO2018078436A1
Application number: PCT/IB2017/001308
Authority: WO
Inventors: 智昭打矢; 良阪口; 任弘高階; 将根津; 崇竹之内
Original assignee: スリ一エムイノべイティブプロパティズカンパニ一
Priority date: 2016-10-31
Filing date: 2017-10-31
Publication date: 2018-05-03

Abstract

Provided is a three-dimensionally shaped thermally conductive molded body (1) and manufacturing method thereof, that can ensure sufficient gap filling properties and contact surface area with regard to heat dissipating components such as heat sinks and the like and heat generating components such as IC chips and the like, without adding excessive stress to these components. The three-dimensionally shaped thermally conductive molded body of a first aspect of the present disclosure contains a thermally conductive material and a silicone-based material, the molded body has a substantially flat bottom surface, and a three-dimensional shaped part located on the inside of the bottom surface, and the height of the three-dimensionally shaped part that is higher than the bottom surface differs in at least two locations (a, b).

Description

Specification

Title of invention: Three-dimensional shape thermally conductive molded body and manufacturing method thereof

[0001] The present disclosure relates to a three-dimensional shape thermally conductive molded body and a method for manufacturing the same.

Background art

[0002] In order to efficiently cool the heat generated by heat-generating components (power transistors, thyristors, etc.) and integrated circuits (ICs, LSIs, etc.) that make up electronic devices, Applying a thick heat dissipation sheet to the gap has been done to improve the heat dissipation of the heat generating parts. Conventional heat-dissipating sheets are inflexible, so that, for example, when thermal expansion occurs, there is a risk of damaging the adjacent elements and substrate due to excessive stress. Therefore, a more flexible heat dissipation sheet has been demanded.

[0003] In Patent Document 1 (Patent No. 3 4 9 2 6 5 6), a predetermined amount of fluid heat conductive grease is injected into a bag-like thin film sheet from its opening, and this heat conduction is performed. Thermally conductive sheet that extends in the form of a thin sheet along the outer shape of the bag, hermetically seals the opening while exhausting the air inside, and shrinks the thin film sheet with hot air, finally shaping it into a thin sheet The manufacturing method is described.

[0004] Patent Document 2 (Patent No. 2 7 2 6 0 7) discloses a heat-dissipating insulating sheet obtained by coating and curing a silicone rubber containing a thermally conductive filler on a mesh-like reinforcing material, and a thermally conductive filler. The uncured addition-type liquid silicone rubber whose hardness after curing with an agent is in the range of 10 to 95 with a F-hardness meter is integrally formed by molding, injection molding or coating molding, A method for producing a heat conductive composite sheet is described in which liquid silicone rubber is cured and combined with a heat insulating sheet.

[0005] Patent Document 3 (Patent No. 2 9 3 8 3 40) discloses a silicone rubber layer containing a thermally conductive filler and having a Asker C hardness of 5 to 50, and the silicone rubber. There is described a thermally conductive composite sheet comprising a porous reinforcing material layer having pores with a diameter of 0.3 mm or more of leno weave contained in the layer. [0006] In Patent Document 4 (Patent No. 3 3 8 2 8 4 2), a plurality of electronic components having different component heights are mounted on a printed wiring board, and what is a printed wiring board in these electronic components? A heat sink is connected to the opposite surface via a heat transfer member made of a material having flexibility and high thermal conductivity, and the surface facing the electronic component in the heat transfer member is flat. A large number of columnar protrusions that gradually increase in thickness from the leading end surface toward the other end on the base side are integrally formed so as to be close to each other, and the leading end surfaces of the columnar protrusions are pressed against the electronic component and are adjacent to each other. An electronic component cooling structure is described in which a heat transfer member is interposed between an electronic component and a heat sink in a state where a V-shaped groove is formed between the electronic components.

Prior art documents

[0007] Patent Document 1: Japanese Patent No. 3 4 9 2 6 5 6

Patent Document 2: Japanese Patent No. 2 7 2 8 6 0 7

Patent Document 3: Japanese Patent No. 2 9 3 8 3 4 0

Patent Document 4: Japanese Patent No. 3 3 8 2 8 4 2

Summary of the Invention

Problems to be solved by the invention

[0008] The ability to fill a gap between a heat-generating component and a heat-dissipating component such as a heat sink in the thermally conductive sheet (hereinafter, sometimes referred to as "gap filling property") can be achieved if the sheet becomes flexible. It is known to improve. However, if the sheet is too soft, it is difficult to maintain the shape of the sheet. In some cases, the constituent material of the sheet that protrudes from the end of the sheet may contaminate adjacent electronic components. It was. A general heat conductive sheet has a sheet shape in which both main surfaces are flat (Patent Documents 2 to 3). In the case of a conventional flexible heat conductive sheet, a polysulfone or the like having poor flexibility is used. Because it was provided with a skin made of plastic material (Patent Document 1), During this period, air-trabbing was likely to occur, and there was a problem that a sufficient contact area could not be secured.

[0009] The present disclosure ensures sufficient gap filling property and contact area for exothermic parts such as IC chips and heat dissipating parts such as heat sinks without applying excessive stress. A three-dimensional shape heat conductive molded body and a method for manufacturing the same are provided.

Means for solving the problem

[0010] According to one embodiment of the present disclosure, including a thermally conductive material and a silicone-based material

A three-dimensional shape heat conductive molded body, the molded body having a substantially flat bottom surface and a three-dimensional shape portion located in the bottom surface, and a height of the three-dimensional shape portion above the bottom surface. There is provided a three-dimensionally shaped thermally conductive molded body that differs in at least two places.

[001 1] According to another embodiment of the present disclosure, a step of preparing a mixture including a thermally conductive material and a silicone-based material, a substantially flat bottom surface, and a three-dimensional shape portion located in the bottom surface And a step of preparing a mold from which a molded body having a height different from the height of the three-dimensional shape portion at least in two places above the bottom is obtained, and an extensible film so as to be in contact with the inner surface of the mold Placing the mold on the mold, pasting the stretchable film on the mold, filling the cavity of the mold with the stretchable film, and optionally forming the bottom of the molded body The step of flattening the substrate, the step of curing the mixture in the mold, and optionally cooling the mold, taking out the three-dimensional shape heat conductive molded article having the stretchable film from the mold, and optionally stretching Possible film is removed, and the shape is arbitrarily attached A method of manufacturing a three-dimensional shape heat conductive molded body is provided, which includes a step of punching a portion that is not formed to obtain a three-dimensional shape heat conductive molded body.

[0012] According to another embodiment of the present disclosure, a first silicone-based material containing a heat conductive material is applied on the stretchable film of a laminated film including a stretchable film and a release film. The process of forming the upper outer layer by curing, and can be extended to the inner surface of the mold after removing the release film of the laminated film with the upper outer layer A step of arranging the laminated film on a mold so that the film can come into contact with the mold, the mold having a substantially flat bottom surface and a three-dimensional shape portion located in the bottom surface, and above the bottom surface The mold can obtain a molded body having different heights in at least two places, a process of bonding the laminated film to the mold, and a cavity of the mold bonded with the laminated film And filling the intermediate member containing the second silicone material containing the heat conductive material, and optionally performing a flattening process on the portion located on the bottom side of the molded body, and optionally peeling A third silicon-based material containing a heat conductive material is applied on the film to form a bottom outer layer, and the bottom outer layer covers the top outer layer and the intermediate member filled in the cavity. A release film including a bottom outer layer; Placing the film on the mold so that the film is the outermost layer, and curing the second silicone material constituting the intermediate member and, if present, the third silicone material constituting the bottom outer layer, After optionally cooling the mold, remove the three-dimensional shape thermally conductive molded body with the stretchable film and the optional release film from the mold, and remove the optional stretchable film and / or the optional release film. Optionally, punching out the upper outer layer portion that does not include the intermediate member and the bottom outer layer portion, if present, to obtain a three-dimensional shape thermally conductive molded body, and manufacturing a three-dimensional shape thermally conductive molded body A method is provided.

According to still another embodiment of the present disclosure, a three-dimensional shape heat conductive molded body including a plurality of protrusion layers and a bottom outer layer, wherein the protrusion layers include a heat conductive material and a silicone material. The bottom outer layer includes a thermally conductive material, a silicone-based material, and a reinforcing base, and the protrusion layer is not in contact with the outer periphery of the bottom surface of the adjacent protrusion layer, so that there is a gap between the adjacent protrusion layers Has been placed,

The following formula (I)

[Number 1]

Qi Y = 1 0 0— X (Ο

[Where α is about 0.70 to about 1.0, X is the compression ratio (%) when the gap is completely filled by the compression deformation of the protruding layer, and Υ is the bottom outer layer This is the ratio (%) of the total area of the bottom surface of the protrusion layer to the total area of the top surface. The three-dimensional shape heat conductive molded body satisfying the above is provided.

[0014] According to still another embodiment of the present disclosure, a step of preparing a mixture including a heat conductive material and a silicon-based material, and forming a protruding layer and a gap of the three-dimensional shape heat conductive molded body A mold that can be stretched, a process in which an extensible film is placed on the mold so as to be in contact with the inner surface of the mold, a process in which the stretchable film is bonded to the mold, and a mold in which the stretchable film is bonded. Filling the cavity with the mixture, and placing the laminate for the bottom outer layer on the release film with the bottom outer layer on the mold so that the release film covers the mixture filled in the cavity and the release film is the outermost layer. A step of placing, a step of curing the mixture and the silicone material of the bottom outer layer, and optionally cooling the mold, and then removing the three-dimensional shape heat conductive composition comprising the stretchable film from the mold and arbitrarily extending F There is provided a method for producing a three-dimensional shape heat conductive molded body, comprising: removing a film to obtain a three-dimensional shape heat conductive molded body.

The invention's effect

[0015] According to the present disclosure, sufficient gap filling property and contact area are ensured for exothermic parts such as an IC chip and heat dissipating parts such as a heat sink without applying excessive stress. A three-dimensional shape heat conductive molded body and a method for manufacturing the same are provided.

[0016] According to the present disclosure, there are provided a three-dimensional shape thermally conductive molded body and a method for producing the same, which are excellent in preventing protrusion from the end portions of the constituent materials.

[0017] According to the present disclosure, the contact area with the adherend can be increased, and the three-dimensional shape heat conduction is excellent in heat dissipation, tear resistance, stress relaxation (flexibility), assembly, and the like. A molded article and a method for producing the same are provided.

[0018] According to the present disclosure, a three-dimensional shape heat conductive molded body excellent in heat resistance and a method for producing the same are provided. [0019] According to the present disclosure, there is provided a three-dimensional shape heat conductive molded body excellent in gap filling property and a method for manufacturing the same even when, for example, the heights of a plurality of exothermic parts are different.

[0020] According to the present disclosure, a method for producing a three-dimensional shape thermally conductive molded body that can be molded using an extremely flexible material is provided.

[0021] The above description should not be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.

Brief Description of Drawings

[0022] FIG. 1 is a cross-sectional view of a three-dimensional shape thermally conductive molded body according to an embodiment of the present disclosure.

FIG. 2 is a diagram schematically illustrating a process of forming a three-dimensional shape thermally conductive molded body using a vacuum thermocompression bonding apparatus.

FIG. 3 is a perspective view of a three-dimensional shape thermally conductive molded body according to an embodiment of the present disclosure.

FIG. 4 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 5 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 6 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 7 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 8 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 9 is a perspective view of a three-dimensional shape thermally conductive molded body according to another embodiment of the present disclosure.

FIG. 10 is a cross-sectional view of a three-dimensional shape thermally conductive molded body according to still another embodiment of the present disclosure.

FIG. 1 1 is a perspective view of a three-dimensional shape thermally conductive molded body according to still another embodiment of the present disclosure. FIG. 12 is a schematic diagram of the measurement principle of thermal resistance.

FIG. 13 is a perspective view of a three-dimensional shape thermally conductive molded body according to still another embodiment of the present disclosure.

FIG. 14 is a perspective view of a three-dimensional shape thermally conductive molded body according to still another embodiment of the present disclosure.

BEST MODE FOR CARRYING OUT THE INVENTION

[0023] The three-dimensional shape thermally conductive molded body in the first embodiment is a three-dimensional shape thermally conductive molded body including a thermally conductive material and a silicone-based material, and the molded body is substantially flat. It has a bottom surface and a three-dimensional shape portion located in the bottom surface, and the height of the three-dimensional shape portion above the bottom surface is different in at least two places. Since this three-dimensional shape thermally conductive molded body has a predetermined three-dimensional shape portion, a sufficient contact area can be ensured without applying excessive stress to the adherend to be applied.

[0024] In the three-dimensional shape thermally conductive molded body according to the first embodiment, at least a part of the three-dimensional shape portion may be covered with an upper outer layer containing a silicone material. By providing such an upper outer layer, it is possible to improve the protrusion prevention property at the end of the molded body.

[0025] In the three-dimensional heat conductive molded body according to the first embodiment, a nonwoven fabric may be present on the bottom surface side. If the nonwoven fabric is embedded on the bottom side of the molded body, the stretchability of the molded body in the planar direction is suppressed, and there is no problem such as cracking when the molded body is peeled off from the mold. Can be improved.

[0026] In the three-dimensional shape heat conductive molded body according to the first embodiment, at least a part of the shape of the three-dimensional shape portion may be substantially dome-shaped or substantially kamaboko-shaped. The three-dimensional shape portion having such a shape can further secure a sufficient contact area with the adherend to be applied.

[0027] In the three-dimensional shape thermally conductive molded body according to the first embodiment, the shape of the three-dimensional shape portion may substantially match the shape of the adherend to which the shape portion is applied. By substantially matching the shape of the adherend to which the three-dimensional shape portion is applied, it is sufficient for the adherend. A sufficient contact area can be secured, and the stress on the adherend can be reduced.

[0028] The three-dimensional shape thermally conductive molded body according to the first embodiment includes a bottom outer layer constituting a bottom surface, an upper outer layer disposed so as to cover the bottom outer layer, and between the bottom outer layer and the upper outer layer. And the upper outer layer, the intermediate member, and the bottom outer layer may include a silicone-based material. By using the molded body having such a configuration, the flexibility of the molded body and the contact area with the adherend can be freely designed according to the intended use.

[0029] In the three-dimensional shape heat conductive molded body in the first embodiment, the upper outer layer and the bottom outer layer, or the bottom outer layer and the intermediate member may be made of the same material and integrated. By setting it as such a structure, the molded object excellent in adhesiveness can be obtained.

[0030] In the three-dimensional shape heat conductive molded body according to the first embodiment, the upper outer layer includes a silicone rubber, the intermediate member includes a silicone gel, and the bottom outer layer includes a silicone rubber or a silicone gel. Good. If the upper outer layer containing silicone rubber covers, for example, an intermediate member that is flexible and easily deformed, it is possible to improve the flexibility of the molded body and to prevent the protrusion from the end. Since the upper outer layer has rubber elasticity, for example, if pressure is applied to the molded body from the outside, the intermediate member of the silicone gel can be easily deformed, but if the pressure is removed, the deformed intermediate member is The work can be reverted to its original shape by the restoring force associated with the rubber elasticity of the outer layer.

[0031] In the three-dimensional shape thermally conductive molded body according to the first embodiment, the intermediate member may be more flexible than the upper outer layer and / or the lower outer layer. By adopting such a configuration, the gap filling property of the molded body can be improved.

[0032] The three-dimensional shape thermally conductive molded body in the first embodiment may have different tackiness between the bottom surface and the surface portion of the three-dimensional shape thermally conductive molded body excluding the bottom surface. Such a molded article having tackiness is easily reworked because it adheres to one of the adherends without breaking during rework.

[0033] The manufacturing method of the three-dimensional shape thermally conductive molded body in the first embodiment A step of preparing a mixture containing a functional material and a silicone-based material, a substantially flat bottom surface, and a three-dimensional shape portion located in the bottom surface, wherein the height of the three-dimensional shape portion above the bottom surface is at least 2 A step of preparing a mold from which different molded bodies can be obtained at different locations, a step of placing an extensible film on the die so as to be in contact with the inner surface of the die, a step of attaching the extensible film to the die, A step of filling the cavity of the mold bonded with the stretchable film with a mixture, and optionally performing a flattening process on the bottom portion of the molded body, and a step of curing the mixture in the mold, and optionally After the mold is cooled, the three-dimensional shape heat conductive molded body having the stretchable film is taken out of the mold, the stretchable film is arbitrarily removed, the part not arbitrarily attached with the mold shape is punched out, and the three-dimensional shape heat is removed. Conductivity And a step of obtaining a configuration, the. Another method for producing a three-dimensional shape thermally conductive molded body in the first embodiment is a first method comprising a thermally conductive material on an extensible film of a laminated film including an extensible film and a release film. Applying a silicone material and curing to form the upper outer layer; and after removing the release film of the laminated film having the upper outer layer, the laminated film is brought into contact with the mold inner surface. The mold is a step of placing on a mold, and the mold has a substantially flat bottom surface and a three-dimensional shape portion positioned in the bottom surface, and the height of the three-dimensional shape portion above the bottom surface is at least 2 A second silicone containing a thermally conductive material in a step of bonding a laminated film to the mold, and a cavity of the mold laminated with the laminated film. Material Filling the intermediate member containing the material, and optionally performing a flattening process on the portion located on the bottom side of the molded body, and optionally, a third silicone containing a thermally conductive material on the release film A base material is applied to form a bottom outer layer, and the peeling film includes the bottom outer layer so that the bottom outer layer covers the top outer layer and the intermediate member filled in the cavity. A step of arranging on the mold so as to be a surface layer, a step of curing the second silicone material constituting the intermediate member, and a third silicone material constituting the bottom outer layer, if any, and any After cooling the mold, a three-dimensional shape heat conductive molded body having an extensible film and an optional release film is removed from the mold. Remove, optionally stretchable film and Z or optional release film, and optionally punch out the upper outer layer part that does not contain the intermediate member and the bottom outer layer part if present. And obtaining a molded body.

[0035] Since these manufacturing methods are formed using a mold having a predetermined shape, a three-dimensional shape thermally conductive molded body can be accurately produced even if a flexible material is used.

[0036] The three-dimensional shape thermally conductive molded body according to the second embodiment includes a plurality of protrusion layers and a bottom outer layer, the protrusion layer includes a heat conductive material and a silicone-based material, and the bottom outer layer includes: Including a thermally conductive material, a silicone-based material, and a reinforcing substrate, and the protruding layer is not in contact with the bottom surface outer peripheral portion of the adjacent protruding layer, and is disposed so as to have a gap between the adjacent protruding layers;

The following formula (I)

[Equation 2] α Y = 1 0 0— X (I)

[Where α is about 0.70 to about 1.0, X is the compression ratio (%) when the gap is completely filled by the compression deformation of the protruding layer, and Υ is the bottom outer layer This is the ratio (%) of the total area of the bottom surface of the protrusion layer to the total area of the top surface. Is satisfied. Since this three-dimensional shape heat conductive molded body has a predetermined projection layer and a gap, it can reduce the compressive stress on the adherend as compared with the conventional flat heat radiating sheet, and has a heat radiating property and tear resistance. Stress relaxation property (flexibility), assembly property, etc. can be improved.

[0037] In the three-dimensional shape heat conductive molded body in the second embodiment, the widths of the gaps can be made substantially uniform. By adopting such a configuration, it is possible to uniformly fill the gap with the protruding layer portion that compresses and expands in the horizontal direction. Therefore, it is possible to form a contact surface with less voids on the adherend after compression. it can.

[0038] In the three-dimensional shape heat conductive molded body according to the second embodiment, the upper surface of the protrusion layer is substantially the same. It may be a flat surface. When the upper surface of the projection layer is a substantially flat surface, it becomes easy to form a contact surface with few voids on the adherend after compression deformation of the molded body.

[0039] The three-dimensional shape thermally conductive molded body according to the second embodiment has a shape of the substantially flat surface of the projection layer as a substantially regular triangle, a substantially square, a substantially regular pentagon, a substantially regular hexagon, a substantially rectangular shape, or a substantially rectangular shape. The projection layer may have a cross-sectional portion along each side of the shape, and the adjacent sides in the shape of the adjacent projection layer may be in a substantially parallel state. The protrusion layer having such a structure is easy to be filled in the adjacent gap by the protrusion layer portion that compresses and expands in the horizontal direction, and forms a uniform contact surface with less voids against the adherend application surface after compression. It becomes easy.

[0040] In the three-dimensional shape thermally conductive molded body in the second embodiment, the taper angle of the protrusion layer can be set to about 80 ° to about 90 °. Such a protruding layer is excellent in mold releasability, and after compression, it becomes easier to form a uniform contact surface with less voids relative to the adherend application surface.

[0041] The three-dimensional shape thermally conductive molded body in the second embodiment is a projection layer anchor

The C hardness can be about 0 to about 30. Since the protrusion layer having such hardness is excellent in flexibility, it is excellent in gap filling property, increase in the contact area with respect to the adherend, or unevenness following property due to compression.

C0042] The three-dimensional shape thermal conductive molded body in the second embodiment is applied to an adherend.

The contact area when compressed by 50% can be increased by about 40% or more compared to the contact area when the molded body is applied to the adherend without being compressed. A molded body exhibiting such performance is excellent in stress relaxation for the adherend, and more easily forms a uniform contact surface with less voids on the adherend application surface after compression.

[0043] three-dimensional shape heat conductive body in the second embodiment may have a protrusion layer 5 Roh inch ² or more. With a molded body having such a configuration, sufficient heat dissipation can be exhibited with respect to the adherend.

[0044] In the three-dimensional shape thermally conductive molded body in the second embodiment, the thickness of the bottom outer layer is about 0.5 mm or less, and the thickness of the three-dimensional shape thermally conductive molded body is about 4. O mm or less. It can be done. In general heat dissipation sheets, the compressive stress increases as the thickness decreases. However, since the molded body of the present disclosure has a predetermined protrusion layer and a gap, even if it is such a thickness, the molded body has excellent stress relaxation properties against the adherend, and after compression, the adherend application surface On the other hand, since it is easy to form a uniform contact surface with few voids, sufficient heat dissipation can be exhibited on the adherend.

[0045] A method for producing a three-dimensional shape thermally conductive molded body according to the second embodiment includes a step of preparing a mixture containing a thermally conductive material and a silicone-based material, and a protruding layer of the three-dimensional shape thermally conductive molded body. And a step of preparing a mold capable of forming a gap, a step of arranging an extensible film on the mold so as to be in contact with the inner surface of the mold, a step of bonding the extensible film to the mold, and an extensible film Filling the cavity into the cavity of the above-mentioned mold, and a laminate for the bottom outer layer having the bottom outer layer on the release film, covering the mixture with the bottom outer layer filling the cavity, and the release film being the outermost layer A step of placing the mold on the mold so that the mixture and the silicone material of the bottom outer layer are cured, and optionally a three-dimensional shape thermal conductivity comprising the stretchable film after cooling the mold Removed form from the mold, removing the extendible film arbitrary, and a step of obtaining a three-dimensional shape heat conductive body, the. Since such a manufacturing method is formed using a mold having a predetermined shape, even if a flexible material is used, a three-dimensional shape heat conductive molded body can be produced with high accuracy.

[0046] In the method for producing a three-dimensional shape thermally conductive molded body according to the first or second embodiment, the stretchable film is made of polyolefin resin (polyethylene resin (for example, low density polyethylene resin, medium density polyethylene resin). ), A copolymer of polypropylene and polyethylene, etc.), a polymethylpentene resin (TPX (registered trademark) resin), an ionomer resin, and at least one resin selected from fluorine-based resins. A resin laminate may be used. A film containing such a material is excellent in deep drawability, mold releasability, and releasability from a silicone-based material, so that a three-dimensional shape heat conductive molded body can be produced with higher accuracy.

[0047] The following is a more detailed description for the purpose of illustrating representative embodiments of the present invention. The present invention is not limited to these embodiments.

In the present disclosure, the “three-dimensional shape portion” means a portion of the three-dimensional shape heat conductive molded body that is located above the bottom surface of the molded body.

[0049] In this disclosure, "substantially" means including variations caused by manufacturing errors and the like, and intended to allow a fluctuation of about 20% in soil.

[0050] In the present disclosure, "dome shape" means a substantially circular shape when viewed from above, and the cross section of the center line of the substantially circular shape is a substantially semicircular cross section or a section as described in FIG. One of the outer edges of these cross-sections has a shape that is further cut inwardly from the bottom surface in the vertical direction (eg, along the first height a). It means you may. In the present disclosure, “kamaboko” means that when viewed from above, at least one end of a substantially rectangular shape or a substantially rectangular shape is a substantially semicircular shape or a substantially elliptical shape, and the long side or long axis of these shapes. The cross-section at the intermediate position is a substantially semicircular cross-section or a cross-section as shown in FIG. 1, and either one of the outer ends of these cross-sections is directed inward from the bottom toward the inside. (For example, along the first height a) This means that the shape may be further cut.

[0051] In the present disclosure, "bottom side" means less than about half of the maximum height of the three-dimensional shape portion located above the bottom surface or about 13 or less.

[0052] The three-dimensional shape thermally conductive molded body of one embodiment of the present disclosure is a three-dimensional shape thermally conductive molded body including a thermally conductive material and a silicone material, and the molded body is substantially It has a flat bottom surface and a three-dimensional shape portion located in the bottom surface, and the height of the three-dimensional shape portion above the bottom surface is different in at least two places. Hereinafter, the three-dimensional shape thermally conductive molded body having such a configuration may be referred to as “first three-dimensional shape thermally conductive molded body” or “first molded body”.

[0053] FIG. 1 is a cross-sectional view of a three-dimensionally shaped thermally conductive molded body having a three-layer structure according to an embodiment of the present disclosure. As shown in FIG. 1, the three-dimensional shape thermally conductive molded body 1 includes a bottom outer layer 2, an intermediate member 3, and a top outer layer 4, and has a first height 'a and a second height b. Is different in at least two places in the height of the three-dimensional shape above the bottom Intended to be. Here, when the silicone materials used for the bottom outer layer 2, the intermediate member 3 and the upper outer layer 4 are all the same, it can be regarded as a one-dimensional three-dimensional shape heat conductive molded body. If the silicone material used for the outer layer 2 and the intermediate member 3, the middle part, the material 3 and the upper outer layer 4, or the bottom outer layer 2 and the upper outer layer 4 is the same, the heat conduction of the two-layer structure Can be regarded as a molded product. In the manufacturing process of the molded body, for example, a top outer layer, an intermediate member, and a bottom outer layer (which may include a nonwoven fabric impregnated with a silicone-based material) are sequentially laminated and cured. If the layers are later integrated using the same silicone-based material and the layer interface cannot be distinguished, the molded body can be regarded as a single layer structure.

[0054] The silicone material is not particularly limited, but silicone gel and silicone rubber can be used. When the molded body has a multilayer structure, a different kind of silicone gel may be used, or silicone gel and silicone rubber may be used in combination. Silicone gel has excellent flexibility, and silicone rubber has excellent anti-extrusion properties.

[0055] (Silicone gel)

Silicone gels can be used, such as heat-curing type or room-temperature curing type, and those having a curing mechanism of condensation type or addition type. However, it is easy to adjust the cross-linking density and to make it flexible. A silicone gel obtained from an addition-type silicone composition is preferred. The group bonded to the silicon atom is not particularly limited. For example, an alkyl group such as a methyl group, an ethyl group, and a propyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a vinyl group, and a allyl group. In addition to aryl groups such as alkenyl groups, phenyl groups, tolyl groups, etc., those in which hydrogen atoms of these groups are partially substituted with other atoms or linking groups can be mentioned.

[0056] The method for producing the addition reaction type (or cross-linked) silicone gel used in the present invention is not particularly limited, but usually, organohydrodiene polysiloxane (a-1) and alkenyl polysiloxane (a- 2) and the presence of catalyst It can be obtained by hydrosilylation reaction (addition reaction) in the presence. There are two types of addition reaction curable silicone gel compositions that can form such silicone gels: one-part curable and two-part curable. The liquid curable composition can provide a flexible gel by heating after mixing the two liquids.

[0057] (a-3) Addition reaction catalyst

As an addition reaction catalyst, an addition reaction between a alkenyl group bonded to a silicon atom in the (a-1) component and a hydrogen atom bonded to the silicon atom in the (a-2) component (hydrosilylation reaction) Any catalyst known to promote the process can be used. For example, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and vinyl siloxane, platinum-based catalysts such as chloroplatinic acid 2-ethyl hexanol solution, tetrakis (卜 -phenylphosphine) palladium, paradioxide Palladium-based catalysts such as a mixture of mukuro and black phenyl phosphine, and platinum group metal-based catalysts such as rhodium catalyst can be used.

[0058] The addition amount of the addition reaction catalyst can be appropriately adjusted in consideration of reactivity and the like. For example, the addition amount of the addition reaction catalyst is about 0 with respect to the total amount of the component (a-1) and the component (a-2). It can be used in the range of 1 ppm or more and about 1 OO ppm or less (catalyst metal element conversion).

[0059] The silicone gel adjusts the flexibility of the silicone gel by changing the crosslinking density of the silicone gel by appropriately adjusting the blending ratio of (a-1) to (a-3), the crosslinking temperature and time, etc. can do.

[0060] Silicone gels include, for example, MQ resin type tackifying components, addition of non-reactive adhesive components, length of side chains of non-crosslinked functional groups, types of terminal functional groups, etc. It may be adjusted to develop the desired tackiness.

[0061] (Silicone rubber)

As the silicone rubber, either an addition reaction type or a condensation type can be used. As an addition reaction type silicone rubber, the crosslink density of the above addition reaction type silicone gel is increased to increase the elasticity of rubber (extensive when load is applied, excluding load) It is possible to use a device that exhibits the property of returning to its original position. A condensation-type silicone rubber is one that undergoes a hydrolytic condensation reaction by cross-linking by reacting with moisture in the atmosphere. Examples of the hydrolytic functional groups possessed by this condensed type reactive silicone rubber include, for example, alkoxy groups (de-alcohol type), iso-probenoxy groups (de-acetone type), methyl ethyl ketoxime groups (de-aged xim) Type) and acetoxy group (deacetic acid type), but from the viewpoints of high curing speed and low odor of the released substance, the deacetone type or dealcohol type is preferred.

[0062] (Thermal conductive material)

The thermally conductive material may be insulative or conductive. Insulating heat conductive materials include nitrogen compounds such as boron nitride, aluminum nitride, and silicon nitride, aluminum oxide (alumina), magnesium oxide, zinc oxide, silicon oxide, beryllium oxide, titanium oxide, and copper oxide. , Metal oxides such as cuprous oxide, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, magnesai 卜

(Magnesium carbonate), carbon compounds such as silicon carbide and diamond, silica, talc, my strength, ceramics such as kaolin, bentonite and pie mouth ferrite, titanium boride, calcium titanate, etc. can be used.

Of these, aluminum oxide (alumina), aluminum hydroxide, zinc oxide, boron nitride, and aluminum nitride are preferred from the viewpoint of thermal conductivity and the like. Boron nitride is composed of c-BN (cubic structure), w-BN (Uruthite structure), h-BN (hexagonal structure), r-BN (rhombohedral structure), t-BN (turbulent layer). Any structure such as (structure) may be used. Examples of the shape of boron nitride include scaly ones and aggregates thereof, and any of them can be used.

[0064] Examples of conductive thermal conductive materials include graphite, force bon black, graphite, carbon fiber (pitch and PAN), force bon nanotube (CNT), force — Bonn nanofiber (CNF) ), Metal compounds such as silver, copper, iron, nickel, aluminum, titanium or metal alloys containing these, stainless steel (SUS), conductive metal oxides such as zinc oxide doped with different elements, Metal compounds such as moss can be used. An insulating material such as silica is covered with a conductive heat conductive material to make it conductive, or a conductive heat conductive material is covered with an insulating material such as silicon to make it insulating. Can also be used as a thermally conductive material.

[0065] These thermally conductive materials can be used alone or in combination of two or more.

For the shape of the heat conductive material, various shapes can be used, for example, fiber shape, plate shape, scale shape, rod shape, granular shape, rod shape, tube shape, curved plate shape, needle shape, curved plate shape. , Needles and the like. These heat conductive materials may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, oxidation treatment and the like.

[0066] The total content of the heat conductive material in the three-dimensional shape heat conductive molded body is about 30% by mass or more, about 50% by mass or more, or about 8 depending on the type of the heat conductive material. 0% by mass or more, approximately 95% by mass. / ₀ or less, or about 90% by mass or less. If the molded body has a multilayer structure, the content in each layer may be other than the above range as long as the total content of the entire molded body is in the above range, and the content in each layer is It may be the same or different.

[0067] The heat dissipation performance (thermal conductivity) of the three-dimensional shape thermally conductive molded body of the present disclosure is about 1.0.

O W / m K or higher, or about 1.2 O WZ m K or higher. This value includes the interfacial thermal resistance.

[0068] The average particle size of the thermally conductive material is about 0.1 jm or more, about .0 or more, or about 0.3 μ_ηι or more, about 20.00 Aim or less, about 10 0 xm or less, Or about 70 m or less. The thermally conductive material can be used in combination with at least two particles having different average particle sizes. With such a configuration, the thermal conductivity is improved because the thermally conductive material having a small particle diameter is filled between the large particle diameters and filled in a close packed manner. The average particle size and particle size distribution of the thermally conductive material can be measured with an electron microscope, a laser one-diffracted light scattering device, or the like. For example, when two particles having different average particle diameters are used in combination, two peaks are observed in the particle size distribution in a silicone material containing these particles. Therefore By confirming the number of particle size distribution peaks in the silicone material, it is possible to confirm how many particles having different average particle diameters are contained in the silicone material.

[0069] Silicone-based materials further include additives such as flame retardants, pigments, dyes, fillers, reinforcing materials, leveling agents, antifoaming agents, dispersants, curing accelerators, reactive diluents, and solvents. May be included. The blending amount of these additives can be appropriately determined within a range not impairing the effects of the present invention.

[0070] The intermediate member of the three-dimensional shape thermally conductive molded body has a first force when the intermediate member is formed into a sheet having a thickness of about 1 O mm. The hardness by a C hardness meter is about 30 or less, about 2 or less or about 8 or less, or about 0 or more.

[0071] The three-dimensional shape heat conductive molded body may have a single layer, two layers, or three layers.

From the viewpoint of expressing desired flexibility, in the case of a one-layer structure, it is preferable that the whole is composed of a silicone gel. In the case of a two-layer structure, any two of the bottom outer layer 2, the intermediate member 3 and the upper outer layer 4 may be composed of the same silicone gel, and the remainder may be composed of different silicone gels or silicone rubbers. Alternatively, the bottom outer layer 2 and the upper outer layer 4 may be made of the same silicone rubber, and the intermediate member 3 may be made of silicone gel. From the viewpoint of flexibility and prevention of protrusion from the end, the upper outer layer 4 or the upper outer layer 4 and the bottom outer layer 2 are preferably made of silicone rubber. In the case of a three-layer structure, different silicone materials can be used for the bottom outer layer 2, the intermediate member 3 and the upper outer layer 4, respectively. As in the case of the two-layer structure, it is preferable that the upper outer layer 4 or the upper outer layer 4 and the bottom outer layer 2 are made of silicone rubber from the viewpoint of flexibility and prevention of protrusion from the end. A molded body having a two-layer or three-layer structure in which the intermediate member 3 is more flexible than the upper outer layer 4 and / or the lower outer layer 2 is excellent in preventing protrusion from the end. Among them, the two-layer or three-layer molded body that uses silicone rubber for the upper outer layer 4 or the upper outer layer 4 and the bottom outer layer 2 is a highly flexible silicone that protrudes from the end as an intermediate member. Even if the base material is used, the intermediate member 3 is covered with the upper outer layer 4 made of at least silicone rubber. Therefore, the intermediate member is less likely to leak from the end due to the restoring force of the silicone rubber.

[0072] The three-dimensional shape portion above the bottom surface of the three-dimensional shape heat conductive molded body is not particularly limited as long as the height is different in at least two or three places. Among them, a three-dimensional shape part having a substantially dome shape or a substantially semi-cylindrical shape as shown in FIGS. 1 and 2 is preferable. With such a shape, in particular, when the surface of the adherend to be applied is flat, the top portion having a substantially dome shape or a substantially semi-cylindrical shape first adheres to the flat surface of the adherend, and then molded together with pressing. The three-dimensional shape of the body is flattened from the top to the outside so that the three-dimensional shape of the body is crushed and deformed, and the air between the adherend and the three-dimensional shape is pushed outward. Since it adheres to the surface, air does not enter between the adherend and the three-dimensional shape portion, and the contact area of the three-dimensional shape thermally conductive compact to the adherend can be improved. This effect is exhibited when the upper outer layer contains a silicone-based material, and other plastic materials with poor flexibility are mixed with air even if they have the same three-dimensional shape, A sufficient contact area could not be obtained.

[0073] FIGS. 3 to 9 show examples of specific shapes of the three-dimensional shape heat conductive molded body, but the shape of the molded body is not limited to these. The molded body in FIGS. 3 to 9 has an approximately dome-shaped or approximately semi-cylindrical three-dimensional shape, and therefore has better air bleedability than a conventional flat, single-walled thermally conductive molded body. is there. Among them, the larger the molded body, the more the molded body having a plurality of three-dimensional shapes, as shown in FIGS. 5 to 9, specifically, two or more, three or more, or five or more, The problem of entraining air (bubbles) at the contact part with heat sinks or heat-generating parts such as heating elements can be further reduced. The size, number, placement location, etc. of the three-dimensional shape part in the molded body can be appropriately set in consideration of the shape, size, etc. of the parts to which the molded body is applied. The part and the approximately three-dimensional shape part that is substantially kamaboko may coexist.

[0074] The three-dimensional shape thermally conductive molded body of the present disclosure has a high three-dimensional shape portion above the bottom surface. Therefore, the stress applied to the various parts to be applied can be reduced as compared with the conventional flat sheet-shaped heat conductive molded body. Specifically, when the height of the three-dimensional shape part is used as a reference, the load when the height is compressed to, for example, 80% (load when compressed at 20%) is a flat sheet shape. It becomes smaller than the load when it is compressed at the same ratio using the heat conductive molded body. The load at the time of 20% compression may be about 95% or less, about 90% or less, or about 85% or less as compared to a conventional flat sheet-shaped heat conductive molded body.

[0075] When the application surface of the adherend to which the three-dimensional shape thermally conductive molded body is applied is not substantially flat and has an irregular shape, the three-dimensional shape portion of the molded body has the shape of the adherend. The shape may be approximately the same. For example, it is possible to minimize the stress on each element and maximize the contact area by molding the heat conductive molded body that covers the entire electronic substrate according to the shape of each element on the substrate. it can. Furthermore, for example, even if the adherend is like a coil, it is possible to easily wrap the coil with a three-dimensional shape heat conductive molding without gaps by using a three-dimensional shape like a coil punching die. be able to.

[0076] The size of the three-dimensional shape thermally conductive molded body can be appropriately determined according to the adherend to be applied. When the three-dimensional shape heat conductive molded body has a multilayer structure, the thickness of the top outer layer and the bottom outer layer is about 10 / xm or more in consideration of flexibility, prevention of protrusion from the end, strength, etc. It may be about 50 / xm or more, about 500 m or less, or about 300 m or less.

[0077] In the three-dimensional shape heat conductive molded body, a reinforcing base material such as a woven fabric, a knitted fabric, or a non-woven fabric may be incorporated on the bottom surface side so as not to be exposed from the bottom surface of the molded body. If the reinforcing base is present on the bottom surface side of the molded body, the stretchability of the molded body in the planar direction is suppressed, the strength of the molded body is improved, and cracks when the molded body is peeled off from the mold, etc. Trouble can be prevented. Among these, non-woven fabrics are preferable because they are excellent in the impregnation properties of silicone materials. Nonwoven fabrics are easily impregnated with silicone materials, and the constituent fibers can be fixed with silicone materials. Even if it is thinner than the above, it can have a strength equal to or greater than these reinforcing base materials. As a material for the reinforcing substrate, glass, vinylon, alamide, nylon, polyolefin, polyester, acrylic, and the like can be used. However, since flame retardancy can be imparted, glass is preferable. The nonwoven fabric may have a thickness of about 20 tm or more, or about 40 jam or more, and may be less than about 0.2 mm or less than about 0.1 mm.

[0078] In the three-dimensional shape heat conductive molded body, the tackiness of the bottom surface of the molded body and the surface portion of the molded body excluding the bottom surface may be different. The molded body having such tackiness is easily reworked because it adheres to one of the adherends without breaking during rework. The tackiness of the three-dimensional shape heat conductive molded body can be appropriately adjusted depending on the surface treatment, the use of different materials such as silicone rubber and silicone gel, and the difference in the blending amount of the adhesive component.

[0079] Although the manufacturing method of the three-dimensional shape thermally conductive molded body of the present disclosure will be exemplarily described, the manufacturing method of the three-dimensional shape thermally conductive molded body is not limited thereto. For example, the following method exemplifies a method employing a vacuum thermocompression bonding device for bonding an extensible film, but is not limited to this method, and a vacuum molding method, a film insert molding method, or the like can also be used. .

[0080] The method for producing the three-dimensional shape thermally conductive molded body 60 can be produced, for example, by the following method (Fig. 2).

[0081] On the stretchable film of the laminated film including the stretchable film and the release film, the first silicone material containing the heat conductive material is applied and cured to form the upper outer layer. Curing is not particularly limited, and heat curing, electron beam curing, and the like can be employed.

A mold 20 having a predetermined three-dimensional shape as shown in FIG. 2 (A) is prepared. As shown in FIG. 2 (B), the exemplary vacuum thermocompression bonding apparatus 30 has a first vacuum chamber 31 and a second vacuum chamber 32 on the upper and lower sides, respectively, and between the upper and lower vacuum chambers. A jig for setting the upper outer laminated film 10 to be attached to the mold 20 is provided. The lower vacuum chamber 3 1 has a lifting platform 3 that can be moved up and down. A partition plate 34 and a pedestal 33 are installed on 5 (not shown), and the mold 20 is set on the pedestal 33. As such a vacuum thermocompression bonding apparatus, a commercially available apparatus such as a double-sided vacuum molding machine (manufactured by Fuse Vacuum Co., Ltd.) can be used.

[0083] As shown in FIG. 2 (B), first, in a state where the first vacuum chamber 3 1 and the second vacuum chamber 32 of the vacuum thermocompression bonding apparatus 30 are released to atmospheric pressure, between the upper and lower vacuum chambers, Set the stretchable film with the peelable film removed and the upper outer layer laminated film 10 with the upper outer layer so that the stretchable film is on the mold 20 side. Set the mold 20 on the pedestal 33 in the first vacuum chamber 3 1.

[0084] Next, as shown in Fig. 2 (C), the first vacuum chamber 31 and the second vacuum chamber 32 are closed, the pressure is reduced, and the inside of each chamber is evacuated (atmospheric pressure is 1 atm). In this case, for example, about O atm). After that, or simultaneously with the vacuum, the upper outer layer laminated film 10 is heated. Next, as shown in FIG. 2 (D), the elevator 35 is raised and the mold 20 is pushed up to the second vacuum chamber 32. The heating can be performed by, for example, a lamp heater incorporated in the ceiling portion of the second vacuum chamber 32. The heating temperature can generally be about 50 ° C or higher, or about 130 ° C or higher, about 180 ° C or lower, or about 160 ° C or lower. The degree of vacuum in the reduced-pressure atmosphere can be about 0.110 atm or less, about 0.05 atm or less, and about 0.01 atm or less with atmospheric pressure of 1 atm.

[0085] The heated upper outer layer laminated film 10 is pressed against the surface of the mold 20 and stretched. Thereafter or simultaneously with stretching, the inside of the second vacuum chamber 32 is pressurized to an appropriate pressure (eg, 3 atm to 1 atm) as shown in FIG. 2 (E). The upper outer laminated film 10 heated by the pressure difference is in close contact with the exposed surface of the mold 20, stretches following the three-dimensional shape of the exposed surface, and is in close contact with the surface of the mold 20 in a peelable manner. Form a coating. After reducing the pressure and heating in the state of FIG. 2 (C), the inside of the second vacuum chamber 32 can be pressurized and the exposed surface of the mold 20 can be covered with the upper outer laminated film 10 as it is.

[0086] After that, the upper and lower first vacuum chambers 31 and 32 are again opened to atmospheric pressure. Then, the mold 20 covered with the upper outer layer laminated film 10 is taken out. As shown in FIG. 2 (F), the edge of the upper outer laminated film 10 that is in close contact with the surface of the mold 20 is trimmed to obtain an integrated product 40 including the upper outer laminated film 10 and the mold 20. obtain.

[0087] Next, in the hollow part 1 1 of the one-piece 40, a second series containing a heat conductive material is formed.

Fill the corn-based material and perform a flattening process using a blade or the like as necessary to form the intermediate member 12. At this stage, the second silicone material is cured, taken out from the unitary product 40, and if necessary, the stretchable film is removed and punched to obtain a three-dimensional shape heat conductive molded body. it can. In the exemplary embodiment of FIG. 2, as shown in FIG. 2 (G), on the intermediate member 1 2,

,, '―-

The configuration to which the bottom outer layer 13 is applied is illustrated. In this embodiment, the bottom outer layer 13 is formed by applying a third silicon-based material containing a heat conductive material on a release film (not shown), and the bottom outer layer 13 is formed by laminating the upper outer layer. A release film including the bottom outer layer 13 is disposed so that the release film is the outermost layer so as to cover the film 10 and the intermediate member 12 filled in the cavity portion 11, and the final integrated product 50 Get. Here, when forming the bottom outer layer 13 on the release film, a reinforcing base material such as a nonwoven fabric is applied on the release film, and a third silicone material is applied and impregnated on the base material to form the bottom portion. The outer layer 1 3 can also be obtained. If necessary, after flattening the part located on the bottom side of the molded body with a blade, a rubber roller, etc., the second and third sili- s constituting the intermediate member 12 and the bottom outer layer 13 are formed. Curing corn-based material. From the viewpoint of adhesion, it is preferable to cure the intermediate member 12 and the bottom outer layer 13 at the same time. For curing, various curing methods such as heat curing and electron beam curing can be employed.

[0088] After optionally cooling the final integrated product 50, the three-dimensional shape thermally conductive molded body having the stretchable film and the optionally present release film is taken out of the mold 20 and the three-dimensional shape thermally conductive molding is taken. The body 60 can be obtained. If necessary, stretchable film, release film may be removed, intermediate member not included, upper outer layer part and bottom outer layer part, if present, appropriately punched, individual 3D shape heat A conductive molded body can also be obtained.

[0089] If all of the first to third silicone-based materials containing the heat conductive material are the same material, they can be regarded as a single-layer molded article, and two of the three types are the same material. If it is, it can be regarded as a two-layered molded body, and if all three types are different materials, it can be regarded as a three-layered molded body.

[0090] A three-dimensionally shaped thermally conductive molded body having a single layer structure can also be produced, for example, by the following method.

[0091] Instead of the upper outer layer laminated film 10 described above, the stretchable film is set in a vacuum heating pressure bonding apparatus 30 and the stretchable film is peelably bonded to the mold 20 in the same manner as described above. Thus, an integrated product 40 including the stretchable film and the mold 20 is obtained.

[0092] Next, the cavity portion 1 1 of the integrated product 40 is filled with a silicone-based material containing a heat conductive material, and is subjected to a flattening treatment using a blade or the like as necessary. Harden the material.

[0093] After optionally cooling the mold, the three-dimensional shape heat conductive molded body having the stretchable film can be taken out of the mold, and a one-dimensional three-dimensional shape heat conductive molded body can be obtained. If necessary, the stretchable film may be removed, and an appropriate three-dimensional shape heat conductive molded body can be obtained by performing appropriate punching.

[0094] The stretchable film used in the method for producing a three-dimensional shape thermally conductive molded body has, for example, extensibility so that it can be deep-drawn, and can be separated from the silicone material. The material is not particularly limited as long as it has a material containing polyethylene, such as polyethylene (for example, low density polyethylene resin, medium density polyethylene resin), polyolefin resin such as polypropylene and polyethylene copolymer, polymethylpentene resin (TPX ( (Registered Trademark) Resin), Ionomer Mono Resin, Fluorine Resin, etc. can be used. These materials can be used alone or in combination, and may be in the form of a single layer film or a laminated film. A surface treatment such as a mold release treatment may be appropriately applied to the film surface. [0095] Another embodiment of the present disclosure is a three-dimensional shape thermally conductive molded body (hereinafter, sometimes referred to as "second three-dimensional shape thermally conductive molded body" or "second molded body"). Examples are shown in Figures 10, 11, 13 and 14. The three-dimensional shape heat conductive molded body includes a plurality of protrusion layers and a bottom outer layer, the protrusion layer includes a heat conductive material and a silicon-based material, and the bottom outer layer includes a heat conductive material and a silicone-based material. And the projecting layer is not in contact with the outer peripheral portion of the bottom surface of the adjacent projecting layer, and is arranged so as to have a gap between the adjacent projecting layers. The following formula (I)

[Equation 3]

Gf Y = 1 O O-X (I)

[Where α is about 0.70 to about 1.0, X is the compression ratio (%) when the gap is completely filled by the compression deformation of the protruding layer, and Υ is the bottom outer layer It is the ratio (%) of the total area of the bottom surface of the protrusion layer to the total area of the top surface. Is satisfied.

[0096] The above-described materials can be used as the heat conductive material, the silicone material, and the reinforcing base material used in the protrusion layer and bottom outer layer of the second three-dimensional shape heat conductive molded body. . In such a molded body, it is preferable to use a silicone gel as a silicone-based material from the viewpoint of stress relaxation, contact area, unevenness followability, and the like.

[0097] As illustrated in FIGS. 10, 11, 1 3, and 14, the protruding layer of the second three-dimensional shape thermally conductive molded body is in contact with the outer peripheral portion of the bottom surface of the adjacent protruding layer. There is no gap between adjacent projection layers. The protrusion shape of the protrusion layer is not limited to the following, but can be at least one selected from a substantially cylindrical shape, a substantially prismatic shape, a substantially truncated cone shape, and a substantially truncated pyramid shape. In addition, for example, as illustrated in FIG. 13 or FIG. 14, a protrusion layer (hereinafter referred to as these protrusions) arranged in a substantially linear shape, a substantially wavy shape or a substantially zigzag shape with respect to the main surface of the bottom outer layer The layer is called “substantially linear protrusion layer”, “substantially wavy protrusion layer” or “substantially zigzag protrusion layer”. There is a case. In addition, as the cross-sectional shape when the protrusion layer is cut perpendicularly to the bottom outer layer, a protrusion layer having a substantially square shape, a substantially rectangular shape, or a substantially isosceles trapezoidal shape can be employed. The substantially linear protrusion layer, the substantially wavy protrusion layer, or the substantially zigzag protrusion layer may be formed continuously as illustrated in FIG. 13 or FIG. 14, or may be formed intermittently. Also good. For example, in the case of a three-dimensional shape heat conductive molded body as illustrated in FIG. 13 or FIG. 14, one side of the molded body is the X axis, and one side perpendicular to the X axis is the y axis. When the thickness direction of the z-axis is the z-axis, the substantially linear projection layer, the substantially wavy projection layer, or the substantially zigzag projection layer is formed substantially parallel to the X axis (substantially perpendicular to the y axis). It may be formed substantially parallel to the y-axis (substantially perpendicular to the X-axis), or may be formed with an angle with respect to the X-axis or the y-axis. Here, “wavy” means a smooth wave shape such as a sine wave, while “zigzag” means a shape that bends like a saw blade. From the viewpoint of increasing the contact area with the adherend, the projection layer is preferably a substantially prismatic projection layer, a substantially truncated pyramid projection layer, a substantially linear projection layer, or a substantially wavy projection layer. The upper surface of the protrusion layer may be substantially dome-shaped as described above, but is preferably a substantially flat surface from the viewpoint of increasing the contact area with the adherend. The shape of the flat surface may be a substantially circular shape, a substantially regular triangle, a substantially square, a substantially regular pentagon, a substantially regular hexagon, a substantially rectangular shape, or a substantially wave shape. From the viewpoint of increasing the contact area with the adherend, the shape of the flat surface is preferably a substantially regular triangle, a substantially square, a substantially regular pentagon, a substantially regular hexagon, a substantially rectangular, or a substantially wave shape. In the case of a protruding layer having a flat surface, the protruding layer has a cross-sectional portion along each side of the flat surface shape, and adjacent sides in the flat surface shape of the adjacent protruding layer are substantially parallel. It is preferable that it exists in a state. The protrusion layer having such a structure is easily filled in the adjacent gap by a portion that is compressed and expanded in the horizontal direction (hereinafter, sometimes referred to as an “expanded portion”), and has a small gap with respect to the adherend application surface. It becomes easier to form a uniform contact surface that is not present.

Since the protruding layer is formed so as to satisfy the following formula (I), the second molded body has excellent stress relaxation properties against the adherend and is in contact with the adherend. The area can be improved.

[Number 4ϋ α Υ = 10 Ο-Χ (I)

[Where α is about 0.70 to about 1.00, X is the compression ratio (%) when the gap is completely filled by the compression deformation of the protruding layer, and Υ is the upper surface of the bottom outer layer. This is the ratio (%) of the total area of the bottom surface of the projection layer. ]

α is a coefficient that varies depending on the material constituting the protruding layer and the compression ratio, and can be calculated by the following experiment, for example. First, a cylindrical sample is prepared by punching a sheet with a predetermined thickness with a 44.3 mm punch. Measure the diameter of the upper surface of the cylindrical sample before compression (initial diameter) and the maximum diameter (compressed diameter) of the cylindrical sample after compressing the cylindrical sample by crushing it by 1 mm using a glass plate, etc. To do. Here, the maximum diameter of the cylinder means the diameter of the circular part that is most widened in the horizontal direction between the top surface and the bottom surface of the cylindrical sample. From the measured diameters, calculate the area of the circular part of the cylindrical sample before and after compression, and the area ratio before and after compression corresponding to the above Y (%) (the top surface area before compression and the maximum area after compression) ) Is calculated. Subsequently, the compression ratio (initial thickness (mm) of 1 mmZ cylindrical sample) when the cylindrical sample is compressed by 1 mm, corresponding to the above X (%), is calculated. The values of X and Y are expressed by the following formula (I I)

[Equation 5] a = (100— X) / Y (II) can be introduced to find α. As an example, Table 1 below shows the calculated α results for the cylindrical samples 1 to 3. 1]

α is about 0.70 or more, about 0.72 or more, about 0.75 or more, about 0.77 or more, about 0.80 or more, or about 0.82 or more, and about 1.00 or less. It can be a range. X is the compression ratio (%) when the gap is completely filled by the compressive deformation of the protruding layer, and is not limited to the following range, but is about 20% or more, about 25% or more, or about 30% The range may be about 75% or less, about 70% or less, or about 65% or less. Υ is the ratio (%) of the total area of the bottom surface of the projection layer to the total area of the top surface of the bottom outer layer. As a method for obtaining wrinkles in a three-dimensional shape thermally conductive molded body having a plurality of projection layers, referring to a mold table for obtaining a three-dimensional shape thermally conductive molded body, a size of at least 1 m X lm ( 1 m ² ) 3D shape thermal conductive molding is displayed on a personal computer, and the area A of the bottom surface of the projecting layer of the sheet is calculated, and (area AX 1 00) / (excluding the projecting layer) Y (%) can be obtained from the total area (1 m ² )) of the upper surface of the sheet. Needless to say, the sheet of the three-dimensional shape thermally conductive molded body having a size of at least 1 m × 1 m may be a real sheet. Or, for example, in the case of a three-dimensional shape thermally conductive molded body provided with a hexagonal column projection layer illustrated in FIG. 11, one hexagonal column is arbitrarily selected from a plurality of hexagonal columns, and the hexagonal column Measure the diameter (C) of the circumscribed circle of the regular hexagon (hereinafter sometimes referred to as “inner regular hexagon”) that is the bottom of Next, a regular hexagon that is half the gap width (A) (hereinafter sometimes referred to as “outer regular hexagon”) is derived from each side of the inner regular hexagon, and the diameter of the circumscribed circle of the outer regular hexagon is specified. (C + A). Calculate the area of the inner regular hexagon and the outer regular hexagon based on the diameter of each circumscribed circle, and obtain Y (%) from (area of the inner regular hexagon X 1 00) Z (area of the outer regular hexagon) You can also. The value of Y by such a method is derived from the minimum unit of one protrusion layer. And the size and the shape and size of the gap are substantially equal, Y can be obtained by this method.

[0102] The taper angle (0) of the protrusion layer can be about 80 ° or more or about 82 ° or more, about 90 ° or less, or about 88 ° or less. Such a projecting layer is excellent in mold releasability, and after compression, it becomes easier to form a uniform contact surface with few voids with respect to the adherend application surface. Here, the taper angle (0) of the protrusion layer is formed by a cross section along each side of the flat surface shape on the upper surface of the protrusion layer and the upper surface of the bottom outer layer as shown in FIG. Means angle.

[0103] The protrusion layer has a hardness of about 30 or less, about 20 or less, or about 10 or less when the material constituting the protrusion layer is formed into a sheet having a thickness of about 1 Omm. It may be about 0 or more. Since the protruding layer having the Asker hardness in such a range is excellent in flexibility, it is excellent in gap filling property, increase in the contact area with respect to the adherend, or unevenness following property due to compression.

[0104] The second three-dimensional shape thermally conductive molded body has five protruding layers, Z inch ² or more, 1

Can have 0 pieces / inch ² or more, or 1 2 pieces Z inch ² or more. With the molded body having the related structure, sufficient heat dissipation can be exhibited with respect to the adherend.

[0105] The maximum height from the upper surface of the bottom outer layer to the upper surface of the protruding layer may be about 0.5 mm or more, or about 1. Omm or more, about 3.5 mm or less, or about 3. Omm or less.

[0106] The gap formed between the protrusion layers in the second three-dimensional shape thermally conductive molded body 1 1

4 is provided with a width A at the bottom surface of the gap as illustrated in FIG. 10, and therefore, compared with a molded body having a gap like a V-shaped groove without a related width, The molded body has better tear resistance. When comparing the molded body in which the protrusion layer is applied so as to have the gap of the present disclosure (the former aspect) and the molded body in which the protrusion layer is applied so as to have a gap like a V-shaped groove (the latter aspect), In the latter mode, adjacent projecting layers are closer, and the number of projecting layer parts that can be compressed and expanded in the horizontal direction is smaller than in the former mode. . As a result, in the latter mode in which the ratio of the projecting layer that can be compressed is low, there are restrictions on the size of the unevenness of the adherend to be applied. However, the former mode of the present disclosure compresses the projecting layer compared to the latter mode. In addition, since the degree of possibility is high and the degree of freedom of unevenness tracking increases, there is an advantage that the range of selection of usable adherends is widened. From the viewpoint of facilitating the formation of a uniform contact surface with few voids with respect to the adherend application surface, the width of the gap is preferably substantially uniform.

[0107] The bottom outer layer of the second three-dimensional shape thermally conductive molded body is formed of a reinforcing base material such as a nonwoven fabric between the silicone material layers (10 4, 10 8) as shown in FIG. A laminated structure including the layers 10 6 may be used, or a structure in which a reinforcing material is impregnated with a silicone material and integrated may be used. When the composition containing the silicone material and the heat conductive material used in the bottom outer layer is the same as the composition used in the protrusion layer, the second three-dimensional shape heat conductive molding provided with the protrusion layer and the bottom outer layer The body can be regarded as an integrated product. In this case, the bottom outer layer can be regarded as a portion located below the cross section in the bottom direction of the gap (excluding the release film if it exists).

[0108] A conventional flat heat dissipation sheet generates compressive stress on the compression surface during compression accompanying application of the sheet to an adherend (eg, an IC chip), and the surface near the periphery of the adherend. Tensile stress, which is a reaction in the direction, is generated. Since the adherend may be damaged by these stresses, a heat dissipation sheet having a concavo-convex shape has been developed to alleviate the stress. However, since the conventional heat radiation sheet uses a material with poor flexibility in order to maintain the concave and convex shape, a void portion is formed in the concave portion of the heat radiation sheet and the contact area is reduced. In some cases, heat dissipation was also reduced. In the second three-dimensional shape heat conductive molded body of the present disclosure, the bottom outer layer includes a reinforcing base material such as a nonwoven fabric, and the tear strength of the molded body can be improved. As a material, it is possible to use only a silicone gel that is softer than silicone rubber and excellent in gap filling and unevenness followability, and it can be applied to an adherend after compression rather than a conventional heat dissipation sheet with an uneven shape. The contact area can be further increased and the heat dissipation can be further improved. [0109] When a bottom outer layer that does not include a reinforcing base material is employed, for example, when a molded body is applied between two adherends and compressed and bonded together, the bottom outer layer is peeled off from the bottom outer layer side. Sometimes, it peeled off from the protruding layer side, and the molded body sometimes broke. However, since the second molded body of the present disclosure has the bottom outer layer including the reinforcing base material, the molded body can be peeled from the protruding layer side in a state where the bottom outer layer is stuck to the adherend during rework. Therefore, it has the advantage of excellent rework workability. The tensile strength of the second molded body is preferably about 14 NZ cm 2 or less, about 12 NZ cm ² or less, or about 10 N / cm ² or less from the viewpoint of reworkability.

[0110] The thickness of the bottom outer layer is approximately 0.5 mm or less or approximately from the viewpoint of strength or heat dissipation.

0.4 mm or less, and can be about 0.05 mm or more, or about 0.1 mm or more.

[0111] In the second three-dimensional shape thermally conductive molded body of the present disclosure, the contact area when the molded body is applied to the adherend and compressed by 50% does not compress the molded body onto the adherend. Compared to the contact area when applied to, it can be increased by about 40% or more, about 45% or more, or about 50% or more. A molded body exhibiting such performance is excellent in stress relaxation for the adherend, and more easily forms a uniform contact surface with less voids on the adherend application surface after compression.

[0112] The stress relaxation property of the second three-dimensional shape thermally conductive molded body is more effective as the total area of the molded body on the adherend application surface side (total area of the upper surface of the bottom outer layer) increases. be able to. From the viewpoint of stress relaxation, the total area on the adherend application surface side of the second three-dimensional shape thermally conductive composition (total area of the top surface of the bottom outer layer) is about 50 cm ² or more, about 100 cm ² Or about 20 O cm ² or more.

[0113] From the viewpoint of heat dissipation, the thickness of the second three-dimensional shape thermally conductive molded body is about 4.0 mm or less, about 3.5 mm or less, about 3. Omm or less, or about 2.5 mm. Can be about 0.1 mm or more, or about 0.55 mm or more.

[0114] The compressive stress at the time of about 50% compression of the second three-dimensional shape thermally conductive molded body is about 10 NZ cm ² or less.

[0115] The thermal resistance of the second three-dimensional shape thermally conductive molded body can be about 1.0 KNOW or less.

[0116] The second three-dimensional shape thermally conductive molded body of the present disclosure can be manufactured in the same manner as described above, but the manufacturing method of the three-dimensional shape thermally conductive molded body is not limited thereto. I can't. For example, the following method exemplifies a method that employs a vacuum thermocompression bonding apparatus for laminating an extensible film, but not limited to this method, a vacuum molding method, a film insert molding method, or the like can also be used. it can.

[0117] The second three-dimensional shape thermally conductive molded body can be manufactured, for example, by the following method.

[01 18] Instead of the upper outer layer laminated film 10 shown in FIG. 2, the stretchable film is set in the vacuum thermocompression bonding apparatus 30 so that the stretchable film can be peeled by the same method as described above. Bonded to the mold that can form the protrusion layer and gap of the three-dimensional heat-conductive molded body of 2 to obtain an integral product including the stretchable film and the mold.

[01 19] A reinforcing base material such as a non-woven fabric is disposed on the release film, and a mixture containing a heat conductive material and a silicon-based material is applied onto the reinforcing base material with a knife coater having a predetermined gap interval. And the laminated body for bottom outer layers provided with a bottom outer layer is obtained.

[0120] Next, the hollow portion of the integrated product is filled with a mixture containing a heat conductive material and a silicone-based material that is the same as or different from the mixture used in the production of the bottom outer layer, and a blade or the like is used as necessary. A flattening process is performed, and the bottom outer layer laminate is placed on the mold so as to cover the mixture in which the bottom outer layer is filled in the cavity and the release film is the outermost layer, and then the silicone material is cured.

[0121] After optionally cooling the mold, the three-dimensional shape heat conductive molded body provided with the stretchable film can be taken out of the mold to obtain a second three-dimensional shape heat conductive molded body. If necessary, the stretchable film and / or the release film may be removed, or a punching process may be appropriately performed to obtain a three-dimensional shape heat conductive molded body having a predetermined shape.

[0122] Stretchable fill used in a method for producing a three-dimensionally shaped thermally conductive molded body As the system, the same use as described above can be used.

[0123] The three-dimensional shape thermally conductive molded body of the present disclosure includes a vehicle and a lithium ion battery.

(For example, in-vehicle lithium-ion batteries), used in household electrical appliances, computer equipment, etc. For example, between a heat-generating component such as an IC chip and a heat-dissipating component such as a hinge sink or a hinge pipe It can be used as a heat-dissipating article that can be disposed so as to fill the gap between the heat-generating parts and efficiently transfer heat generated from the heat-generating parts to the heat-dissipating parts. Since the three-dimensional shape heat conductive molded body of the present disclosure can be designed freely in shape and size, it can be used as an alternative to potting materials for circuit boards, for example, for heat generating parts with complex shapes such as coils. However, it can also be used.

Example ,

[0124] In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.

[0125] The raw materials used in this example are shown in Table 2 below.

[0126]

[0127] The characteristics of the first three-dimensional shape thermally conductive molded body of the present disclosure were evaluated according to the following methods.

[0128] [Evaluation method] <Assasser c hardness evaluation>

Wasker rubber hardness tester C type (manufactured by Kobunshi Keiki Co., Ltd.) was used to measure the washer force C hardness of the evaluation sample in accordance with SRI IS 01 01, which is a standard of the Japan Rubber Association.

[0129] <Evaluation of compressive load>

The compressive load was measured with a Tensilon tester using a jig with a size of 35 mm x 40 mm. Place the evaluation sample on the Tensilon testing machine so that it is located in the center of the jig, move the jig attached to the load cell downward at a speed of 0. SmmZ, and when the evaluation sample is compressed 20% The jig was stopped with and the load at that time was measured.

[0130] <Evaluation of thermal conductivity 1>

The thermal conductivity of large samples (Examples 1, 2, and Comparative Example 2) was measured using a QTM-D3 and a probe (PD-13N) manufactured by Kyoto Denshi Kogyo Co., Ltd. 0-chome 1 / 1-03 measures the thermal conductivity by a method called the unsteady thin wire heating method. The probe (sensor) consists of a single heating wire and thermocouple stretched in a straight line. When a constant current is passed through the heating wire, heat is generated and the temperature of the heating wire rises exponentially. In samples with high thermal conductivity (metals, etc.), the heat moves quickly and escapes to the sample side, so the temperature of the heating wire decreases. Conversely, for samples with low thermal conductivity (such as heat insulation materials), the heat does not escape easily, so the temperature of the heating wire rises significantly. Thus, the temperature rise of the heating wire is related to the thermal conductivity of the sample and is expressed by the following equation (1). In other words, the thermal conductivity of the sample can be obtained from the slope of the temperature rise graph with the time axis as a logarithmic scale.

[Equation 6]

A = q X I n (t a / t ^ / {4πΧ (Τ ^ Τ,)} (1)

(Where S is the thermal conductivity of the sample (W / mK), and q is the unit of the heating wire. The unit length is the calorific value (WZm), and 1 t ₂ is the measurement time (seconds). ^ Is time! : Temperature at t ₂ (K). )

[0131] <Evaluation of thermal conductivity 2>

The thermal conductivity of small samples (Examples 3 to 8 and Comparative Example 3) was measured using ASTM D using a thermal resistance measuring device (TIMT ester 1 400 manufactured by Analysis Tech, Inc.). The thermal resistance / thermal conductivity measurement method according to 5470 was performed. Two aluminum blocks (aluminum plates) were installed between the heater and the cooling plate of the thermal resistance measuring device. A sample was inserted between the aluminum blocks, a predetermined load (compression rate) was applied, and the thermal conductivity was measured. In the measurement, the compression ratio was adjusted so that the sample was in contact with the heater and the cooling plate in almost the same area. The compression ratio was about 30% for all samples.

[0132] <Assembly evaluation>

The assemblability of the evaluation sample was evaluated. "Good" for easy releasability from the liner and easy handling of the sample (not significantly stretched), "Possible" for those that can be peeled from the liner but difficult to handle due to plastic deformation of the sample. Those that could not be peeled were marked as “impossible”.

[0133] Evaluation of reworkability>

Reworkability of small samples (Examples 3 to 8) was evaluated by the following method. The sheet-like samples of Comparative Examples 2 and 3 were evaluated in the same manner as those punched into a 16.5 mm0 cylinder. Two float glass plates of 5 c mX l O cm were prepared. Five samples were placed on the surface of one glass plate so that the bottoms were in contact at equal intervals. Another glass plate was placed on top of it, and a 1 kg weight was placed on top of it to ensure that each sample was evenly loaded. Under the load, these glass plates were left for 24 hours in an open temperature controlled at 150 ° C. Then, it took out from the oven, cooled, and peeled the upper glass plate in the state returned to room temperature. Of the 5 samples, all the samples have no change in shape and are not peeled off the lower glass plate. If the sample remains, “good”, if there is no change in the sample shape and one or more samples are attached to the upper glass plate, “Yes”, if the sample shape is deformed when the glass plate is peeled off Was made “impossible”.

[Example 1]

HIMILAN (registered trademark) 1706, which is an ionomer resin, was melted with a single screw extruder having a diameter of 20 mm and a barrel temperature set to 200 ° C. The molten resin is supplied to a die set at 220 ° C with a screw rotating at 59 rpm, and the molten resin discharged from the die is transported at a speed of 1.8 minutes. PET film (emblem Trademark) S25) was extruded and laminated to produce a 125 tm thick ionomer resin ZPET laminated film.

[0135] 500 g CY— 52— 276 A and 250 g P l a t e l e t s O O

3 was weighed into a 2 L planetary mixer and mixed for 15 minutes at a blade rotation speed of 20 rpm to produce a silicone compound 1A. Similarly, weigh 500 g of CY—52—276 B, 5.0 g of CY 52—005 K, and 2509 of PI ate I ets 003 into a planetary mixer, 15 minutes, blade rotation 20 rpm Was mixed to prepare a silicone compound 1B.

200 g of silicone compound 1 A and 200 g of silicone compound 1 B were weighed into a plastic cup and stirred and mixed with a resin spatula for about 10 minutes to prepare silicone compound 1 A B. The silicone compound 1 A B was coated on the ionomer resin side of the ionomer resin Z PET laminated film with a knife coater. The coated ionomer resin ZP ET laminate film was passed through an oven at 1800C for 18 minutes to cure the silicone, producing a boron nitride-containing silicone rubber sheet 1 for the top outer layer. . The thickness of the silicone rubber layer of the sheet 1 was 2 1 3 Atm.

[0136] 1 21.4 g AX35—125, 48.6 g AX3—75, and 30.0 g SE 1 885 A were weighed into a 225 mL glass bottle. Rotate the material in the glass bottle using a revolution mixer, “Awatori Sotaro”, mix at a rotation speed of 200 Orm for 1 minute, and then degas for 30 seconds to remove the silicone component. Wound 2 A was produced. Similarly, 1 21.4 g of AX35—125, 48.6 g of AX3—75, and 30. Og of SE 1 885 B were weighed into a 225 mL glass bottle. The material in the glass bottle was mixed for 1 minute at a speed of 2000 rpm using Yutaro Awatori, and then defoamed for 30 seconds to prepare silicone compound 2B. 1 Weigh 50 g of silicone compound 2 A and 100 g of silicone compound 2 B in a 300 mL plastic cup and stir and mix with a resin spatula for about 5 minutes to avoid bubbles. Silicone compound 2 AB for the member was produced.

[0137] 1400.00 g of SE 1 701 LT V and 1 4. O g of SE 1 701 LTV catalyst was weighed into a 300 m polystrand and foamed with a plastic spatula for about 5 minutes. The mixture was stirred and mixed so that it did not enter to prepare Silicone Compound 3. Next, the silicone compound 3 was applied onto the release liner YB-2, coated with a knife coater with a knife-liner gap set to 15 OAtm, and the bottom outer layer sheet 1 was coated. Produced.

[0138] The PET film of the boron nitride-containing silicone rubber sheet 1 was removed, and an upper outer laminated film 10 having a two-layer structure made of a deep-drawn ionomer resin and a silicon nitride-containing silicone rubber was produced. A double-sided vacuum molding machine (manufactured by Fuse Vacuum Co., Ltd.) is used as the vacuum thermocompression bonding apparatus 30 as shown in FIG. 2 (B), and an ionomer resin is placed on the aluminum mold 20 installed in the apparatus 30. The upper outer layer laminated film 10 was fixed so that is on the mold 20 side. The heating conditions were set so that the surface temperature of the film 10 was 120 ° C. Next, according to the procedure shown in FIGS. 2B to 2E, the heated film 10 is laminated on the surface of the mold 20 so that no air is caught. An integrated product 40 as shown in F) was produced. Here, the mold 20 has such a shape as shown in FIG. 2 (F) that a 23.5 mm × 90.0 mm × 4.0 mm approximately semi-cylindrical three-dimensional shape can be obtained.

[0139] The hollow part 1 の of the integrated product 40 is filled with the silicone compound 2 AB for the intermediate member, and then air is wound on the filled silicone compound 2 AB. The bottom outer layer 1 was laminated so as not to penetrate. A rubber roller 1 was applied onto the sheet 1 so that the sheet 1 was in close contact with the mold uniformly to produce a final integrated product 50. The final integrated product 50 was left in an oven at 120 ° C. for 20 minutes to heat cure the silicone gel constituting the intermediate member and the bottom outer layer. Next, the final product 50 was removed from the oven, cooled, and the cured substantially kamaboko-shaped three-dimensional shape thermally conductive molded body 60 was removed from the mold 20. Before being hardened by cooling, the outermost layer of the nomer resin layer was removed to obtain an evaluation sample of a substantially kamaboko-shaped three-dimensional shape heat conductive molded body. After injecting silicone compound 2AB for intermediate parts into a 30 mmX4 Omm X 10 mm thick mold coated with YB-2 as the release liner, it was cured in an oven at 120 ° C. The tester thus produced had an Asker C hardness of 0.

Example 2>

75. Og AX3—75 and 25. Og CY52—276A were weighed into a 225 mL glass bottle. The material in the glass bottle was mixed for 1 minute at a rotational speed of 2000 rpm using Yutaro Awatori, and then defoamed for 30 seconds to prepare Silicone Compound 4A. Similarly, 75.09 ₉ 's 3-75, 25.0 g CY52-276 B and 0.25 g CY52-005 K were weighed into a 225 mL glass bottle. The material in the glass bottle was mixed for 1 minute at a speed of 2000 rpm using Awatori Eitaro, and then defoamed for 30 seconds to produce silicone compound 4B. Weigh 80 g of silicone compound 4 A and 80 g of silicone compound 4 B into a 300 mL plastic cup, and stir and mix with a resin spatula for about 5 minutes to prevent foaming. Silico Compound 4 AB Was made. Glass paper GMC 1 0—Mr 6 is placed on YB-2, which is the release liner, then the silicone compound 4 AB is applied onto the glass plate, and the gap between the knife and liner is 1 The bottom outer layer sheet 2 was prepared by impregnating with a knife coater set at 50 Am. Except that the bottom outer layer sheet 2 was used in place of the bottom outer layer sheet 1, a substantially kamaboko-shaped three-dimensional structure was used in the same manner as in Example 1. An evaluation sample of the shape heat conductive molding was obtained. Therefore, as in Example 1, the test piece produced had a first force of 1 C hardness.

[0141] <Example 3>

1 Weigh 50.0 g of silicone compound 2 A and 1 22.7 g of silicone compound 2 B into a 30 OmL plastic cup and mix with a resin spatula for about 5 minutes to prevent foaming. N compound 5 AB was produced. Silicone compound 2 A B instead of silicone. A mold that uses Wind 5 AB and has a shape in which multiple rows of three-dimensional shapes with a diameter of 19 mm and a thickness of 4. Omm are arranged so that they do not overlap in parallel in the vertical and horizontal directions. An evaluation sample of a substantially dome-shaped three-dimensional thermal conductive molded body was produced in the same manner as in Example 1 except that it was used. After injecting silicone compound 5 AB for intermediate parts into a 30mmX40mmX10mm thick mold covered with YB-2 of the release liner, cure in 120 ° C oven. The test piece thus prepared had a first force C hardness of 0.

[0142] <Example 4>

A bottom outer layer sheet 3 was prepared in the same manner as in Example 2 except that silicone compound 3 was used instead of silicone compound 4 A B. Silicone compound 5 AB is used instead of silicone compound 2 AB, the mold is changed to the type used in Example 3, and the bottom outer layer sheet 3 is used instead of the bottom outer layer sheet 3 In the same manner as in Example 2, an evaluation sample of a substantially dome-shaped three-dimensional shape thermally conductive molded body was produced. Therefore, as in Example 3, the test specimen produced had a false force-C hardness of 0.

[0143] <Example 5>

Dyion (registered trademark) THV 500, a fluororesin, was melted with a single screw extruder with a diameter of 2 Omm with the barrel temperature set to 200 ° C—220 ° C-230 ° C-260 ° C. The molten resin was supplied to a die set at 260 ° C, and the molten resin discharged from the die was extruded onto a 75 micron thick PET film for lamination to produce a fluororesin / PET laminated film. Fluororesin layer The thickness was 1 0 0 ^ m.

[0144] Next, 100 0 of silicone compound 2 A and 100 g of silicone compound 2 B were weighed into a 3 0 0 mL polycup, and a resin sno. A silicone compound 6 AB was prepared by mixing the contents with CHIYURA for about 5 minutes without bubbles.

[0145] The silicone compound 6 AB is placed on the release liner YB-2, then the silicone compound 6 AB is applied onto the glass paper GMC10-0 MR6, and the knife and liner are combined. The bottom outer layer sheet 4 was produced by coating and impregnating with a knife coater with a gap set to 1550 tm.

[0146] The PET film of the laminated film was removed to produce a fluororesin film capable of deep drawing. The same vacuum thermocompression bonding equipment as in Example 1 is adopted, and the mold is composed of a plurality of approximately three-dimensional rows with a diameter of 16.5 mm and a thickness of 2.6 mm that are parallel in the vertical and horizontal directions. However, a mold having shapes that are alternately displaced was used. Spray paste 55 (manufactured by Sriem Japan Co., Ltd.) was sprayed on the mold and the solvent was dried before use. Lamination of the fluororesin film to the mold was performed in the same manner as in Example 1.

[0147] Silicone compound 6 AB was poured onto a mold coated with a fluororesin film, and then the bottom outer layer sheet 4 was laminated on the silicone compound coated surface so as not to entrain the wires. The mold covered with the bottom outer layer sheet 4 was pressure-bonded with a rubber neck so that the sheet was evenly adhered to the mold to produce a final integrated product. The final monolith was allowed to stand in an oven at 120 ° C. for 20 minutes, and the silicone gel constituting the molded body was heated and cured. Next, the final integrated product was taken out from the oven and allowed to cool to room temperature. After standing for 1 day, the three-dimensional shape heat conductive molded product was taken out from the mold. Next, the fluororesin film on the surface was peeled off to obtain an evaluation sample of a three-dimensional shape heat conductive molded body having a substantially dome shape with a diameter of 16.5 mm and a thickness of 2.6 mm. Silicone compound 6 AB coated with YB-2 release liner 30 mm After injecting into a mold having a thickness of X4 OmmX 10 mm, the test piece produced by curing in an oven at 120 ° C. had a first strength C hardness of 0.

[0148] Example θ>

1 21.4 g ΑΧ35— 1 25, 48.6 g AX3— 75, 30.0 9 S E 1 885 A was weighed into a 225 ml glass bottle. Next, the contents of the glass bottle were mixed for 1 minute at a rotational speed of 2000 rpm using Awatori Eitaro, and then defoamed for 30 seconds to prepare silicone compound 7A. Similarly, 1 21 · 4 g AX35— 1 25, 48.6 g AX3 — 75, 30. O g SE 1 885 B, 0.0375 g additive “SP 72 97 J in a 225 mL glass bottle Was mixed for 1 minute at a rotation speed of 20000 pm using Awatori Shintaro and defoamed for 30 seconds to prepare Silicone Compound 7 B. 100 g of Silicone Compound 7 A and The silicone compound 7B of 1009 was weighed into a 30 OmL polycup, and the contents were mixed with a resin spatula for about 5 minutes so as not to cause foaming to produce silicone compound 7AB. A bottom outer layer sheet 5 was prepared in the same manner as in Example 5 using silicone compound 7 AB, full-size silicone liner YB-2, and glass paper GMC 10 0-MR 6. Instead of silicone compound 6 AB Same as Example 5 except using silicone compound 7 AB for An evaluation sample of a three-dimensional shape heat conductive molded body having a substantially dome shape with a diameter of 16.5 mm and a thickness of 2.6 mm was obtained by the method described above, and the silicon compound 7 AB was peeled off. Test specimens made by injecting into a 30 mmX40 mmX l 0 mm thick mold coated with YB-2 of the liner and cured in an oven at 120 ° C 1 C hardness was 5 It was.

[0149] Case 7>

1 21.4 g AX35—125, 48.6 g AX3—75, and 30.09 SE 1 885 A were weighed into a 225 mL glass bottle. Next, the contents of the glass bottle are mixed for 1 minute at a speed of 2000 rpm using Awatori Eitaro, and defoamed for 30 seconds to produce silicone compound 8A. did. Similarly, weigh out 1 21 · 4 g of AX35—125, 48.6 g of AX3—75, 30. O g of SE 1 885 B, and 0.075 g of SP 7297. Was used for 1 minute at a rotational speed of 2000 rpm, and defoamed for 30 seconds to prepare silicone compound 8B. Weigh 100 g of silicone compound 8 A and 100 g of silicone compound 8 B into a 3 O OmL plastic cup and mix the contents with a resin spatula for about 5 minutes without foaming. A silicone compound 8 AB was prepared. Using the silicone compound 8 AB, the fluorosilicone liner YB-2, and the glass paper GMC 10—MR 6, a bottom outer layer sheet 6 was prepared in the same manner as in Example 5. Three-dimensional shape thermal conductive molding with an approximate dome shape with a diameter of 16.5 mm and a thickness of 2.6 mm in the same manner as in Example 5 except that silicon compound 8 AB is used instead of silicone compound 6 AB An evaluation sample of the body was obtained. In addition, after injecting silicone compound 8 AB into a 30 mm X 40 mm X 10 mm thick mold coated with YB-2, the release liner, the test piece prepared by curing in an oven at 120 ° C was used. The first force C hardness was 8.

1 21.4 g AX35—125, 48.6 g AX3—75, and 30.0 g S E 1 885 A were weighed into a 225 mL glass bottle. Next, the content of the glass bottle was mixed for 1 minute at a rotation speed of 2000 rpm using Awatori Yutaro, and then defoamed for 30 seconds to prepare silicone compound 9A. Similarly, 1 21.4 g of AX35—125, 48.6 g of A X3—75, 30. O g of S E 1 885 B, 0.150 g of S P 7297

Weighed into a 225 ml glass bottle. Next, the content of the glass bottle was mixed for 1 minute at a rotational speed of 2000 rpm using Awatori Eitaro, and then defoamed for 30 seconds to prepare silicone compound 9B. 100 g of silicone compound 9 A and 100 g of silicone compound 9 B

Weigh in a 300 ml plastic cup and use a plastic spatula for about 5 minutes. Silicone compound 9 AB was prepared by mixing so as not to contain bubbles. Using the silicon compound 9 AB, the fluorosilicone liner YB-2, and the glass separator GMC 10 0-MR 6, the bottom outer layer 7-7 was prepared in the same manner as in Example 5. Three-dimensional shape heat conduction with a substantially dome shape with a diameter of 16.5 mm and a thickness of 2.6 mm in the same manner as in Example 5 except that silicone compound 9 AB is used instead of silicone compound 6 AB An evaluation sample of the molded product was obtained. The test piece was prepared by injecting silicone compound 9 AB into a 30mmX40mmX10mm thick mold coated with release liner YB-2 and then curing in 120 ° C oven. The force C hardness was 30.

[0151] <Comparative Example 1>

Silicone compound 2 AB was applied between two release liners (YB-2), and a 2 mm thick silicone gel sheet was obtained through a knife coater head with the gap between the liners set to 2 mm. . The sheet was then allowed to stand in an oven at 120 ° C. for 20 minutes to cure the silicone gel sheet. Since the cohesive strength of the sheet was very low and could not be removed from the release liner, the various characteristics of the sheet could not be measured.

[0152] <Comparative Example 2>

Apply a silicone compound 6 AB between two release liners (YB-2) and pass a 2 mm thick silicone gel sheet through a knife coater head with a 2 mm gap between the liners. Obtained. Next, this sheet was allowed to stand in an oven at 120 ° C. for 20 minutes to cure the silicone gel. Prepare two sheets from which one of the two liners has been peeled off, and bond the two sheets so that no air bubbles are caught between the layers. A thermally conductive sheet was obtained. Note that the test piece prepared by bonding three sheets of 4 mm thick had a first force C hardness of 0.

[0153] <Comparative Example 3>

Silicone compound 9 AB suitable between two release liners (YB-2) And a 2.6 mm thick silicone gel sheet was obtained through a knife coater head with a gap between the liners set at 2.6 mm. Next, this sheet was allowed to stand in an oven at 120 ° C. for 20 minutes to harden the silicone gel sheet, thereby obtaining a silicone heat conductive sheet for evaluation having a thickness of 2.6 mm. In addition, the Asker C hardness of a test piece prepared by bonding three 2.6 mm thick sheets was 30. For the measurement of compressive stress, a sample punched from this sheet into a cylindrical shape with a diameter of 16.5 mm was used.

[0154] In Examples 1 to 8 and Comparative Examples 1 to 3, the first force C hardness, compressive load (20

Table 3 shows the results of the% load), thermal conductivity 1 and 2, assemblability and releasability.

[0155] [Table 3]

[0156] As shown in Table 3, the three-dimensional shape thermal conductive molded body of the present disclosure exhibits excellent flexibility and compressive stress. In addition, comparing Example 8 with Comparative Example 3, both use the same silicone compound 9 AB and show the same Asker C hardness. The stress of Example 8 shows about 78% of the stress of Comparative Example 3, and Example 8 is lower than Comparative Example 3. As a result, the shape of the molded body reduces the stress when compressed by 20%, that is, the stress applied to various members to which the molded body is applied can be reduced. Suggests that

[0157] The characteristics of the second three-dimensional shape thermally conductive molded body of the present disclosure were evaluated according to the following methods.

[0158] [Evaluation method]

The first force C hardness of the evaluation sample was measured using a C1 rubber hardness meter C type (manufactured by Kobunshi Keiki Co., Ltd.) in accordance with SRI ISO 1001, which is a standard of the Japan Rubber Association.

[0159] <Evaluation of compressive stress>

The compressive stress was measured with a Tensilon tester using a flat plate jig. Place the evaluation sample at the center of the jig so that the 330 mm x 88 mm evaluation sample is compressed, move the jig attached to the load cell downward at a speed of 5. OmmZ, and the evaluation sample is 1 The jig was stopped when it was compressed by 0 mm, and the stress at that time was measured.

[0160] Evaluation of heat resistance>

The thermal resistance value of the evaluation sample was measured with a thermal impedance meter TIM tester manufactured by Analyssi Tetech. The measurement principle of such a device is outlined below.

[0161] The TIM tester can measure the thermal resistance value according to AS TM D 5470. The probe (one sensor) consists of a heater plate, a cooler plate, and multiple thermocouples. 33. Omm cylindrical TIM sample is compressed 1. Omm with heater and cooling plate. When the test starts, a certain amount of heat is applied from the heater plate. Here, the cooler is always cooled with water. After the temperature stabilizes, the heat flux and temperature at the sample interface are calculated from the temperature data obtained from several thermocouples (Figure 12). As a result, the thermal resistance value is calculated from the following equation (2) according to the heat flow and temperature difference between the heater and cooler contacts. [Equation 7]

IftS resistance (K / W) = temperature difference (K) / heat flow (W) (2)

[0162] <Evaluation of tensile bond strength (reworkability)>

The bottom outer layer surface of the evaluation sample is lined with a single-sided adhesive tape (manufactured by Sumitomo 3EM, part number # 85 1 mm). After that, 90 ° peel adhesion was measured according to the procedure specified in JI SZ-0237. The molded product was peeled at a pulling speed of 30 OmmZ.

[0163] <Example 9>

Hi-Millan (registered trademark) 1706, which is an eye-catching resin, was melted with a single screw extruder having a diameter of 2 Omm and a barrel temperature set at 200 ° C. The molten resin is supplied to a drop die set at 220 ° C with a screw rotating at 59 rpm, and the molten resin discharged from the drop die is transported at a speed of 1.8 mZ for a PET film (emblem of 25 microns) (Registered Trademark) S 25) Cast on top to produce 1.25 m thick ionomer resin PET film

[0164] 1 08 g AX 75— 1 50, 36 g A X 35— 1 25, 36 g AX

3—75, 1 g DMS—V22 and 19 g SE 1 885 A were weighed into a 225 mL glass bottle. The material in the glass bottle was mixed for 1 minute at a rotation speed of 2 000 rpm with a rotating / revolving mixer, and then defoamed for 30 seconds to produce a silicone compound 1a. Similarly, 225 ml glass bottles with 108 g AX75—150, 36 g AX35—125, 36 g AX3—75, 1 g DMS—V22 and 19 g SE 1 885 B Similarly, the material in the glass bottle was mixed and defoamed to prepare silicone compound 1b. 1 Weigh 50 g of silicone compound 1 a and 150 g of silicone compound 1 b into a plastic cup, then use a resin spatula for approximately 10 minutes. Manually mixed to make a silicone gel compound 1 ab.

[0165] The PET film was removed from the above-mentioned ionomer resin ZPET laminated film to obtain an ionomer resin film capable of deep drawing. A double-sided vacuum molding machine (manufactured by Fuse Vacuum Co., Ltd.) is used as a vacuum thermocompression bonding apparatus as shown in Fig. 2 (B), and an ionomer resin film is fixed on an aluminum mold installed in the apparatus. did. The heating conditions were set so that the surface temperature of the film would be 120 ° C. Next, according to the procedure shown in FIG. 2 (B) to FIG. 2 (E) described above, the heated film is laminated on the surface of the mold so that air is not entrapped, and shown in FIG. An integrated product was manufactured.

[0166] Glass paper G M C 1 as a reinforcing substrate on Y B-2 as a release film

0—After MR 6 is placed, the silicone gel compound 1 ab is applied onto the glass spacer with a knife coater having a gap interval of 1 5 0 im, and the bottom outer layer is provided with a bottom outer layer. A sheet was obtained.

[0167] Silicone gelco is formed in the hollow part of the integrated product covered with an ionomer resin film.

Compound 1 ab was filled, and then, a laminated sheet for the bottom outer layer was laminated on the filled silicone compound 1 ab so as not to entrain air. A rubber roller was applied on the sheet to flatten the sheet so that the sheet was uniformly adhered to the mold, and a final integrated product was produced. The final monolith was allowed to stand at 120 ° C. for 10 minutes to heat cure the silicone gel. Next, the final integrated product was taken out of the oven and cooled, and the cured three-dimensional shape heat conductive molded body was taken out of the mold so that the ionomer resin film was removed from the mold. Next, before cooling and solidifying, the eye-like resin film was removed from the three-dimensional shape heat conductive molded body, and an evaluation sample of the three-dimensional shape heat conductive molded body was obtained. Here, the mold used has such a shape that a projection layer having an approximately flat hexagonal upper flat surface as shown in Fig. 11 is obtained, and the three-dimensional shape heat conduction obtained from the mold is used. As shown in Table 4, the evaluation sample of the molded product is the gap width (A), the height of the projection layer (B), the diameter of the circumscribed circle on the bottom of the projection layer (C), and the taper angle. , And the number of protrusions per square inch. [0168] <Example 1 0 to 1 1>

Three-dimensional shape satisfying the gap width (A), protrusion layer height (B), circumscribed circle diameter (C), taper angle, and number of protrusions per square inch shown in Table 4. Evaluation samples of Example 10 and Example 11 were obtained in the same manner as in Example 9 except that the mold was changed to a mold capable of obtaining a thermally conductive molded body.

[0169] <Comparative Example 4>

Apply a silicone compound 1 ab between two release liners (YB-2) and pass through a knife coater head with a gap between the liners set to 2.1 mm. A silicone gel was obtained. Next, this sheet was allowed to stand for 20 minutes in an opening at 120 ° C. to cure the silicone gel sheet, and then four sheets were laminated to obtain an evaluation sample having a thickness of 6. Omm.

[0170] <Comparative Example 5>

Silicone compound 1 ab is applied between two release liners (YB-2), with a thickness of 1.5 mm through the knife coat head with the gap between the liners set at 2.1 mm. A silicone gel sheet was obtained. Next, this sheet was allowed to stand in an oven at 120 ° C. for 20 minutes to cure the silicone gel sheet, and then the three sheets were laminated to obtain an evaluation sample having a thickness of 4.5 mm.

[0171] <Comparative Example 6>

Silicone compound 1 ab is applied between two release liners (YB-2), and a 1.5 mm thick silicone is passed through a knife coater head with the gap between the liners set at 2.1 mm. A gel sheet was obtained. Next, this sheet was allowed to stand in an oven at 120 ° C. for 20 minutes to cure the silicone gel sheet, and then an evaluation sample having a thickness of 3 mm was obtained by laminating the two sheets.

[0172] For each of the evaluation samples in Examples 9 to 11 and Comparative Examples 4 to 6, the Asker C hardness, compressive stress (stress at 1 mm compression), thermal resistance (thermal resistance at 1 mm compression) and [] ¾SS ^^^. ¾i ^ fl8Θ8¾〜, I

1) Compression ratio when the gap is completely filled by compressive deformation of the projecting layer (/ 6)

Percentage of the total area of the bottom surface of the protrusions out of the total surface area of the top surface of the outer bottom layer (%)

〔〕〕Four As the thickness decreased, the thermal resistance tended to decrease, but the compressive stress and tensile bond strength tended to increase. As a result, when trying to obtain a molded product having a low thermal resistance with a conventional flat heat dissipation sheet, the compressive stress and the tensile adhesive strength increase, so that the heat dissipation sheet breaks the adherend. Or the reworkability deteriorated. On the other hand, in the case of the second three-dimensional shape thermally conductive molded body of the present disclosure, as can be seen from Examples 9 to 11, the thickness of the molded body is equal to or less than the thickness of the sample of Comparative Example 6. It was confirmed that even in the configuration, in addition to the thermal resistance, the compressive stress and the tensile bond strength can be kept low. Therefore, the second three-dimensional shape thermally conductive molded body of the present disclosure can obtain good thermal conductivity and reduce defects on the adherend as compared with the conventional flat heat dissipation sheet. I understood.

Explanation of symbols

1, 60 0 1st three-dimensional shape heat conductive molding

2, 1 3, 1 1 0 Bottom outer layer

3, 1 2 Intermediate member

4 Upper outer layer

1 0 Upper outer layer laminated film

2 0 type

3 0 Vacuum thermocompression bonding equipment

3 1 1st vacuum chamber

3 2 Second vacuum chamber

3 3 pedestal

3 4 Partition plate

3 5 Lift platform

4 0 Integrated product

5 0 Final integrated product

1 0 0 Second three-dimensional shape thermally conductive molded body

1 0 2 Release film , 1 08 Silicone material Reinforced substrate

Projection layer

Gap

1st height

Second height

Gap width

Projection layer height

Diameter of circumscribed circle on the bottom of the projection layer

The thickness of the second three-dimensional shape heat conductive molded body Taper angle

Claims

ⁿ 0 1 3 C 8

WO 2018/078436 53 PCT / IB2017 / 001308

The scope of the claims

[Claim 1] A three-dimensionally shaped thermally conductive composition comprising a thermally conductive material and a silicone material,

The molded body has a substantially flat bottom surface and a three-dimensional shape portion located in the bottom surface, and the height of the three-dimensional shape portion above the bottom surface is different in at least two places. Original shape heat conductive molding.

[Claim 2] The three-dimensional shape thermally conductive molded article according to claim 1, wherein at least a part of the three-dimensional shape part is covered with an upper outer layer containing a silicone-based material.

[Claim 3] The three-dimensional shape thermally conductive molded article according to claim 1 or 2, wherein the nonwoven fabric is inherently present on the bottom side.

[Claim 4] The three-dimensional shape heat conduction according to any one of claims 1 to 3, wherein at least a part of the shape of the three-dimensional shape portion is substantially dome-shaped or substantially kamaboko-shaped. Molded product.

[Claim 5] The three-dimensional shape heat transfer according to any one of claims 1 to 3, wherein a shape of the three-dimensional shape portion substantially matches a shape of an adherend member to which the shape portion is applied. Conductive molded body.

[Claim 6] The molded body comprises a bottom outer layer constituting the bottom surface, an upper outer layer disposed so as to cover the bottom outer layer, and an intermediate member disposed between the bottom outer layer and the upper outer layer. The three-dimensional shape thermally conductive molded body according to any one of claims 1 to 5, wherein the upper outer layer, the intermediate member, and the bottom outer layer include a silicon-based material.

[Claim 7] The three-dimensional shape thermal conductive molding according to claim 6, wherein the upper outer layer and the bottom outer layer, or the bottom outer layer and the Φ inter-material are re-integrated from the same material. body.

[Claim 8] The three-dimensional shape thermal conductivity according to claim 6 or 7, wherein the upper outer layer includes silicone rubber, the intermediate member includes silicone gel, and the bottom outer layer includes silicone rubber or silicone gel. Molded body. 贿 320 1? / 0 0 1 3 C 8

WO 2018/078436 54 PCT / IB2017 / 001308

[Claim 9] The three-dimensional shape heat conductive molded body according to any one of claims 6 to 8, wherein the intermediate member is softer than the upper outer layer and the bottom outer layer or the bottom outer layer.

[Claim 10] The three-dimensional shape heat according to any one of claims 1 to 9, wherein the bottom surface and the surface portion of the three-dimensional shape heat conductive molded body excluding the bottom surface are different in tackiness. Conductive molded body.

[Claim 1 1] A method for producing a three-dimensional shape thermally conductive molded body, comprising:

A step of preparing a mixture including a thermally conductive material and a silicone-based material; a substantially flat bottom surface; and a three-dimensional shape portion located in the bottom surface, wherein the height of the three-dimensional shape portion above the bottom surface Preparing a mold from which a molded body different in at least two places can be obtained;

Placing an extensible film on the mold so that it can contact the inner surface of the mold;

The step of bonding the stretchable film to the mold, and filling the mixture into the cavity of the mold to which the stretchable film is bonded, and optionally performing a flattening process on the portion that becomes the bottom surface of the molded body The process,

Curing the mixture in the mold;

After optionally cooling the mold, a three-dimensional shape heat conductive molded body provided with the stretchable film is taken out of the mold, optionally the stretchable film is removed, and a portion not arbitrarily attached with the mold shape is punched out A method for producing a three-dimensional shape thermally conductive molded body, comprising: obtaining a three-dimensional shape thermally conductive molded body.

[Claim 12] A method for producing a three-dimensional shape thermally conductive molded body, comprising:

Applying a first silicone-based material containing a heat conductive material on the stretchable film of the laminated film including the stretchable film and a release film, and curing the first silicone material to form an upper outer layer; PC 麵 1 7/0 0 1 3 C 8

WO 2018/078436 55 PCT / IB2017 / 001308

After the release film of the laminated film having the upper outer layer is removed, the laminated film is placed on the mold so that the stretchable film can come into contact with the inner surface of the mold, and the mold is substantially flat A mold having a bottom surface and a three-dimensional shape portion located in the bottom surface, wherein a molded body is obtained in which the height of the three-dimensional shape portion above the bottom surface is different in at least two places; and ,

Bonding the laminated film to the mold;

The cavity of the mold to which the laminated film is bonded is filled with an intermediate member containing a second silicone material containing a heat conductive material, and is optionally flat with respect to the portion located on the bottom side of the molded body Forming a bottom outer layer by applying a third silicon-based material containing a thermally conductive material on the release film, and the bottom outer layer includes the upper outer layer and the cavity. A step of disposing a release film including the bottom outer layer on the mold so that the release film is the outermost layer so as to cover the intermediate member filled in

A step of curing the second silicone material comprising the intermediate member, and a third silicone material comprising the bottom outer layer, if any, and optionally cooling the mold, the stretchable film and optionally The three-dimensional shape heat conductive molded body provided with the release film present is removed from the mold, and optionally the stretchable film and / or the existing release film is removed, and optionally the intermediate member is not included. Punching out the upper outer layer portion and, if present, the bottom outer layer portion, to obtain a three-dimensional shape thermally conductive molded body, and a method for producing a three-dimensional shape thermally conductive molded body.

[Claim 13] A three-dimensional shape thermally conductive molded body comprising a plurality of projecting layers and a bottom outer layer.

Because

The protruding layer includes a heat conductive material and a silicone-based material, 2 C 8

The bottom outer layer includes a heat conductive material, a silicone-based material, and a reinforcing substrate,

The protrusion layer is not in contact with the outer peripheral portion of the bottom surface of the adjacent protrusion layer, and is disposed so as to have a gap between the adjacent protrusion layers.

The following formula (I)

[Equation 1] α? Υ = 100-X (I)

[Where α is from 0.70 to 1.00, X is the compression ratio (%) when the gap is completely filled by compressive deformation of the protruding layer, and の is the total area of the top surface of the bottom outer layer Of this, it is the ratio (%) of the total area of the bottom of the projection layer. ]

Satisfying the three-dimensional shape heat conductive molding.

The three-dimensional shape heat conductive molded body according to claim 13, wherein the gaps have substantially uniform widths.

The three-dimensional shape thermally conductive molded body according to claim 13 or 14, wherein an upper surface of the protruding layer is a substantially flat surface.

The shape of the substantially flat surface is a substantially regular triangle, a substantially square, a substantially regular pentagon, a substantially regular hexagon, a substantially rectangular shape, or a substantially wave shape, and the protruding layer is a cross-sectional portion along each side of the shape. The three-dimensional shape heat conductive molded body according to claim 15, wherein the adjacent sides in the shape of the adjacent projecting layers are in a substantially parallel state.

The three-dimensional shape thermally conductive molded body according to any one of claims 13 to 16, wherein the protrusion layer has a taper angle of 80 ° to 90 °.

The three-dimensional shape thermally conductive molded article according to any one of claims 13 to 17, wherein the protrusion layer has a first force C hardness of 0 to 30.

The contact area when _500/0 compression is applied to a 3D-shaped thermally conductive molded body applied to the adherend is applied without compressing the 3D-shaped thermally conductive molded body to the adherend. PC 20 "/ 0018C8

The three-dimensional shape thermally conductive molded article according to any one of claims 13 to 18, wherein the contact area is increased by 40% or more compared to the contact area when WO 2018/078436 57 PCT / IB2017 / 001308 is applied.

[Claim 20] The three-dimensionally shaped thermally conductive molded article according to any one of claims 1 to 19, which has 5 protruding layers / inch ² or more.

[Claim 21] The thickness of the bottom outer layer is 0.5 mm or less, and the thickness of the three-dimensional shape thermally conductive molded body is 4. Omm or less. Three-dimensional shape heat conductive molded body.

[Claim 22] A method for producing a three-dimensional shape thermally conductive molded article according to any one of claims 13 to 21, comprising:

Preparing a mixture containing a thermally conductive material and a silicone-based material; preparing a mold capable of forming a protruding layer and a gap of a three-dimensionally shaped thermally conductive molded body; and

Bonding the stretchable film to the mold;

Filling the mixture into the cavity of the mold with the stretchable film bonded together;

Placing the laminate for the bottom outer layer comprising the bottom outer layer on the release film on the mold so that the bottom outer layer covers the mixture filled in the cavity and the release film is the outermost layer;

A step of curing the mixture and the silicone material of the bottom outer layer, and optionally cooling the mold, and then removing a three-dimensional shape thermally conductive molded body comprising the stretchable film from the mold, optionally the stretchable film and Removing the Z or the release film to obtain a three-dimensional shape thermally conductive molded body, and a method for producing a three-dimensional shape thermally conductive molded body.

[Claim 23] The stretchable film is at least selected from a polyolefin resin, a polymethylpentene resin, an ionomer resin, and a fluorine resin. The method for producing a three-dimensional shape thermally conductive molded article according to claim 11, 1, 2 or 22, wherein PCT / I32ft 7; non C 3 58 PCT / IB2017 / 001308 contains one resin.