JP2018103586A - Composite laminate and composite laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite laminate that has sufficient thermal conductivity and can suppress transfer onto a process object.SOLUTION: A composite laminate includes:a thermal conductive layer that includes a resin and a carbon material and has a thermal conductivity in the thickness direction of 7.0 W/m K or more; and a coating layer.SELECTED DRAWING: None

Description

  The present invention relates to a composite laminate and a composite laminate sheet, and more particularly to a composite laminate and a composite laminate sheet containing a carbon material.

  In recent years, composite laminates and sheet-like members (composite laminate sheets) made of composite materials having functionality such as thermal conductivity have been used for various applications.

  On the other hand, a thermocompression bonding method is known as a method for bonding and bonding the same or different materials. In the thermocompression bonding method, for example, the materials can be thermally welded by applying heat and pressure at a temperature lower than the melting point of the materials to be bonded and bonded. It is also possible to heat-bond the materials with high adhesion by applying a low melting point adhesive between the materials to be joined and bonded and applying heat and pressure at a temperature below the melting point of the material. . And, in the thermocompression bonding method, usually, a material with an adhesive is optionally laminated between the heating device and the fixture, and heating and pressurization are performed from the side of the heating device facing one material. While performing, the adhesive is melted while transferring heat to the fixture side to which the other material is fixed, and the materials are heat-welded with high adhesion.

  In thermocompression bonding, a composite laminated sheet may be interposed between the heating device and the fixture or between the material and the fixture for the purpose of protecting the material. Conventionally, as a sheet for thermocompression bonding, the component (A) composed of an organopolysiloxane and the component (B) which is a thermally conductive filler composed of a metal silicon pulverized powder, a crystalline silicon dioxide pulverized powder or an aluminum oxide pulverized powder; A silicone rubber sheet containing a component (C) made of carbon black powder for imparting heat resistance and antistatic properties has been proposed (see, for example, Patent Document 1).

Japanese Patent No. 5058938

Here, for example, if vibration energy such as ultrasonic waves is used as a heat source of the heating device, during the thermocompression bonding, the heating device, the fixture, the workpiece, and the thermocompression bonding sheet interposed therebetween are vibrated. Can occur. Due to such vibration, the surface of the sheet may be rubbed against the surface of the workpiece, and the components of the sheet may be transferred to the material. Similarly, not only the thermocompression bonding by ultrasonic waves, but also when the object to be processed and the sheet are brought into close contact under high heat environment in other applications, the components of the sheet are caused to adhere to the object to be processed due to high heat and close contact. In some cases, transcription may occur. If the components of the sheet are transferred to the workpiece, the quality of the workpiece may not be sufficiently improved.
Therefore, the conventional thermally conductive sheet has room for improvement in terms of suppressing the transfer of the constituent components to the workpiece, that is, improving the transfer resistance.

  Then, an object of this invention is to provide the heat conductive composite laminated body and composite laminated sheet which can suppress the transcription | transfer to the workpiece surface.

  The present inventors have intensively studied to achieve the above object. And this inventor can suppress that the component of a heat conductive layer transfers with respect to the workpiece surface by laminating | stacking a coating layer on the heat conductive layer which consists of a material containing resin and a carbon material. It was found anew. Furthermore, the present inventors have found that in a laminate having such a structure, the heat conductivity as a composite laminate can be sufficiently increased by employing a heat conductive layer having a thermal conductivity of a predetermined value or more, The present invention has been completed.

That is, the present invention aims to advantageously solve the above-mentioned problems, and the composite laminate of the present invention contains a resin and a carbon material, and has a thermal conductivity in the thickness direction of 7.0 W / m. -It is characterized by including the heat conductive layer which is more than K, and a coating layer. By disposing the coating layer on the heat conductive layer having a thermal conductivity of a predetermined value or more, the transfer resistance characteristics of the obtained composite laminate can be improved.
In addition, in this invention, "thermal conductivity" can be measured by the method as described in the Example of this specification.

In the composite laminate of the present invention, the coating layer preferably contains a resin having a glass transition temperature of 80 ° C. or higher. When the glass transition temperature of the resin contained in the coating layer is equal to or higher than the lower limit, the transfer resistance of the composite laminate can be further enhanced.
The glass transition temperature of the resin contained in the coating layer can be measured according to JIS K7121.

  In the composite laminate of the present invention, the coating layer preferably contains a fluororesin or an imide resin. If the coating layer contains a fluororesin or an imide resin, the transfer resistance of the composite laminate can be further enhanced.

  In the composite laminate of the present invention, the resin contained in the heat conductive layer is preferably a fluororesin or a silicone resin. If the resin constituting the heat conductive layer contains a fluororesin or a silicone resin, the heat resistance of the composite laminate can be improved.

  In the composite laminate of the present invention, it is preferable that the resin contained in the thermal conductive layer is a thermoplastic fluororesin that is liquid at normal temperature and pressure. If the resin contained in the heat conductive layer is a thermoplastic fluororesin that is liquid at normal temperature and pressure, the flexibility of the composite laminate can be improved.

  Moreover, this invention aims at solving the said subject advantageously, The composite laminated sheet of this invention consists of one of the said composite laminated bodies, It is characterized by the above-mentioned. Such a composite laminated sheet is excellent in transfer resistance.

  ADVANTAGE OF THE INVENTION According to this invention, while having sufficient heat conductivity, the composite laminated body and composite laminated sheet which can suppress the transcription | transfer to the workpiece surface can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The composite laminate sheet of the present invention formed by molding the composite laminate of the present invention into a sheet shape is, for example, in a thermocompression bonding method in which materials are joined and bonded together using a heating device and a fixture. It can be suitably used as a thermocompression-bonding sheet interposed between the tools. Moreover, the composite laminated body of this invention can be used conveniently for all the uses for which the function of contacting with a workpiece and conducting heat is required. For example, the composite laminate of the present invention is a heat-dissipating material, a heat-dissipating component, a cooling component, a temperature-adjusting component, and an electromagnetic shielding component that can be used in various devices and apparatuses; It can be used as a pouch for an individual package product such as a retort food or shampoo. Further, for example, the composite laminate sheet of the present invention can be used in place of a metal member for heat conduction that is used at the time of hot pressing at the time of mounting electronic parts or the like or at the time of mounting automobile parts.

(Composite laminate)
The composite laminate of the present invention includes a resin and a carbon material, and includes a thermal conductive layer having a thermal conductivity in the thickness direction of 7.0 W / m · K or more and a coating layer. If the thermal conductive layer includes a layer containing a resin and a carbon material and having a thermal conductivity in the thickness direction of 7.0 W / m · K or more, the thermal conductivity of the composite laminate can be sufficiently increased. . And if a coating layer is applied with respect to this heat conductive layer, it can suppress effectively that the component of a heat conductive layer transcribe | transfers with respect to another member, and can improve the transcription | transfer resistance of a composite laminated body. .

<Resin>
Here, the resin that can be included in the heat conductive layer is not particularly limited, and examples thereof include a fluororesin, a silicone resin, an acrylic resin, an epoxy resin, and a polyethylene resin. Especially, it is preferable that a heat conductive layer contains a fluororesin or a silicone resin. If the resin constituting the heat conductive layer contains a fluororesin or a silicone resin, the heat resistance of the composite laminate can be improved.

[Fluororesin]
Examples of the fluororesin include a thermoplastic fluororesin that is liquid at normal temperature and pressure, and a thermoplastic fluororesin that is solid at normal temperature and pressure, such as an elastomer obtained by polymerizing a fluorine-containing monomer. Moreover, these fluororesins may be used individually by 1 type, and may use 2 or more types together.
In this specification, “normal temperature” refers to 23 ° C., and “normal pressure” refers to 1 atm (absolute pressure).
In the present invention, rubber and elastomer are included in “resin”.

  From the viewpoint of enhancing the property of adhesion between the heat conductive layer and the coating layer constituting the composite laminate of the present invention (hereinafter, this property is also referred to as “self-adhesive”), a thermoplastic fluororesin that is liquid at normal temperature and pressure Is preferably used. If the self-adhesiveness of the composite laminate is high, the heat conductive layer can be satisfactorily adhered to the coating layer without using an adhesive layer, etc., so that the structure of the composite laminate can be manufactured well. It becomes possible. In addition, since the number of components of the composite laminate can be reduced, when the composite laminate is attached to the heat source, the heat received from the heat source is reduced while the loss during heat conduction is reduced. It can conduct heat in the direction.

[[Thermoplastic fluororesin that is liquid at normal temperature and pressure]]
Examples of commercially available thermoplastic fluororesins that are liquid at room temperature and normal pressure include, for example, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropentene-tetrafluoroethylene terpolymer, and perfluoropropene. Examples thereof include an oxide polymer and a tetrafluoroethylene-propylene-vinylidene fluoride copolymer. Specifically, as a thermoplastic fluororesin that is liquid at room temperature and normal pressure, Viton (registered trademark) LM manufactured by Chemers, Daiel (registered trademark) G-101 manufactured by Daikin Industries, Ltd., Dinion manufactured by 3M Co., Ltd. Commercial products such as FC2210 and SIFEL series manufactured by Shin-Etsu Chemical Co., Ltd. can also be used.
The viscosity of the thermoplastic fluororesin that is liquid at normal temperature and pressure is not particularly limited in terms of good kneadability, fluidity, cross-linking reactivity, and excellent moldability. It is preferably 500 mPa · s or more and 30,000 mPa · s or less, and more preferably 550 mPa · s or more and 25,000 mPa · s or less.
In the present specification, “viscosity” can be measured using a viscometer under the conditions of a temperature of 105 ° C. and an atmosphere of 1 atm and a rotational speed of 6 rpm.

[Solid thermoplastic fluororesin at room temperature and normal pressure]
More specifically, the thermoplastic fluororesin that is solid at normal temperature and pressure includes polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene. -Ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorofluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyvinyl fluoride, tetrafluoroethylene-propylene copolymer Polymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, polytetrafluoroethylene acrylic modified, polytetrafluoroethylene ester modified, polytetrafluoroethylene Epoxy-modified product of Ruoroechiren and silane-modified product of polytetrafluoroethylene, and the like.
Among these, from the viewpoint of workability, the thermoplastic fluororesins that are solid at normal temperature and pressure include polytetrafluoroethylene, acrylic modified polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene. A fluoride-hexafluoropropylene-tetrafluoroethylene copolymer is preferred. Moreover, these may be used individually by 1 type and may use 2 or more types together.

  Examples of commercially available thermoplastic fluororesins that are solid at room temperature and normal pressure include, for example, Daiel (registered trademark) G-300 series / G-700 series / G-7000 series (polyol vulcanized / vinylidene) manufactured by Daikin Industries, Ltd. Fluoride-hexafluoropropylene binary copolymer), Daiel G-550 series / G-600 series (polyol vulcanized / vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer), Daiel G -800 series (peroxide vulcanized / vinylidene fluoride-hexafluoropropylene binary copolymer), Daiel G-900 series (peroxide vulcanized / vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene ternary copolymer) Polymer); AL KYNAR (registered trademark) series (vinylidene fluoride fluororesin) manufactured by EMA, KYNAR FLEX (registered trademark) series (vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene ternary copolymer); .

[Silicone resin]
The silicone resin is not particularly limited, and examples thereof include resins having an organopolysiloxane structure as a main chain. Such silicone resins include a one-component reaction type, a two-component reaction type, a three-component reaction type, and those that react in four or more liquids, and any reaction type silicone resin can be suitably used. . Among them, a two-component reaction type can be suitably used. This is because a two-part silicone resin is superior to a one-part silicone resin from the viewpoint of storage stability, and a two-part silicone resin is superior to a reactive silicone resin having three or more parts from the viewpoint of easy handling. Because. The two-component reactive silicone resin can be a mixture of a main agent and a curing agent. As the two-component reaction type silicone resin, either a two-component condensation reaction type silicone or a two-component addition reaction type silicone may be used, but from the viewpoint of not generating a reaction by-product (outgas), two-component addition It is preferable to use reactive silicone.

  In the two-component addition reaction type silicone, an organopolysiloxane having an alkenyl group is generally used as a main agent, and an organohydrogenpolysiloxane having an SiH group as a crosslinking group is used as a curing agent. By mixing these two liquids and performing an addition reaction (hydrosilylation reaction) under a metal catalyst such as platinum, it is possible to obtain a normal gel silicone (silicone gel) that is a reaction product of the main agent and the curing agent. it can. The metal catalyst may be contained in the main agent or the curing agent, and may be added separately from the main agent and the curing agent.

  The organopolysiloxane as the main agent is not particularly limited as long as it has an alkenyl group in the molecule. Examples of the alkenyl group that the organopolysiloxane has include a vinyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. Among these, it is preferable to have a vinyl group. The structure of the organopolysiloxane is usually a straight chain having a repeating main chain composed of diorganosiloxane units, but may be partially branched.

  Examples of the organic group other than the alkenyl group bonded to the silicon atom of the organopolysiloxane as the main agent include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tert. -Alkyl groups such as butyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; halogenated alkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group Can do. Among them, it is preferable to have a methyl group. As a polyorganosiloxane having a methyl group, for example, dimethylpolysiloxane can be mentioned as an easily available one.

  The organohydrogenpolysiloxane serving as the curing agent is not particularly limited as long as it has a SiH group in the molecule. The structure of the organohydrogenpolysiloxane may be, for example, linear, branched, or cyclic. Moreover, as an organic group couple | bonded with the silicon atom of the organohydrogenpolysiloxane used as a hardening | curing agent, the same thing as what was illustrated as an organic group couple | bonded with the silicon atom of the organopolysiloxane used as the said main ingredient is mentioned.

  A commercially available product may be used as the two-component reactive silicone resin. Commercially available products of two-component reactive silicone include, for example, “TSE-3062A” (main agent) manufactured by Momentive Performance Materials Japan GK and “TSE-3062B” manufactured by the same company as two-component addition reactive silicone. Curing agent).

  The two-component condensation reaction type silicone is usually a room temperature curing type (RTV) that cures at room temperature. On the other hand, there are two-component addition reaction type silicones, room temperature curable type (RTV) and heat curable type (Low Temperature Vulcanizable: LTV) which is cured by heating to 50 to 130 ° C. May be.

[Ratio of resin content]
The content of the resin in the heat conductive layer is preferably 30% by mass or more and more preferably 40% by mass or more with respect to 100% by mass of the total content of the resin and the carbon material described later. 80% by mass or less, and more preferably 70% by mass or less. If the resin content is at least the above lower limit, for example, the flexibility of the heat conductive layer is improved. In addition, although the heat conductivity of a heat conductive layer improves that the content rate of resin is less than 30 mass%, there exists a possibility that the softness | flexibility of a heat conductive layer may fall. Moreover, if the content rate of resin is below the said upper limit, the heat conductivity of a heat conductive layer will improve more.

<Carbon material>
The carbon material is not particularly limited, and a known carbon material can be used. Specifically, as the carbon material, a particulate carbon material, a fibrous carbon material, or the like can be used. Incidentally, the particulate carbon material and the fibrous carbon material may be used either alone or in combination, but from the viewpoint of easily increasing the thermal conductivity of the thermal conductive layer, It is preferable to use at least a particulate carbon material. That is, it is preferable that the carbon material contains at least a particulate carbon material. In addition, it is more preferable to use the particulate carbon material and the fibrous carbon material in combination from the viewpoint of preventing the particulate carbon material from falling off from the thermal conduction layer while further improving the thermal conductivity of the thermal conduction layer. . That is, it is more preferable that the carbon material further contains a fibrous carbon material in addition to the particulate carbon material.

[Content ratio of carbon material]
The content ratio of the carbon material in the heat conductive layer is preferably 20% by mass or more, more preferably 30% by mass or more, and 95% by mass or less with respect to 100% by mass of the resin described above. It is preferable that it is 60 mass% or less. If the content rate of the carbon material in a heat conductive layer is more than the said minimum, a carbon material will orientate better in a heat conductive layer, and carbon materials will contact and form a favorable heat-transfer path | pass. As a result, the thermal conductivity of the heat conductive layer can be increased. Moreover, if the content rate of a carbon material is below the said upper limit, while providing a heat conductive layer with a softness | flexibility, the self-adhesiveness of a composite laminated body can be improved.

[Particulate carbon material]
The particulate carbon material is not particularly limited, and examples thereof include artificial graphite, flaky graphite, exfoliated graphite, natural graphite, acid-treated graphite, expandable graphite, expanded graphite, and the like; carbon black; Can be used. These may be used individually by 1 type and may use 2 or more types together.
Among them, it is preferable to use expanded graphite as the particulate carbon material. This is because the use of expanded graphite can further improve the thermal conductivity of the heat conductive layer.
In the present invention, the aspect ratio (major axis / minor axis) of the particulate carbon material contained in the heat conductive layer is usually 1 or more and 10 or less, and preferably 1 or more and 5 or less. In the present invention, the “aspect ratio” means that the cross section in the thickness direction of the heat conduction layer is observed with an SEM (scanning electron microscope), and for any 50 particulate carbon materials, the maximum diameter (major diameter), It can be determined by measuring the particle diameter (minor axis) in the direction orthogonal to the maximum diameter and calculating the average value of the ratio of the major axis to the minor axis (major axis / minor axis).

[[Expanded graphite]]
Here, the expanded graphite that can be suitably used as the particulate carbon material is, for example, finely expanded after heat-treating expandable graphite obtained by chemically treating graphite such as scaly graphite with sulfuric acid or the like. Can be obtained. And as an expanded graphite mix | blended with the heat conductive layer of the composite laminated body of this invention, EC1500, EC1000, EC500, EC300, EC100, and EC50 (all are brand names) etc. by Ito Graphite Industries, Ltd. are mentioned, for example. It is done.

[[Particle size of particulate carbon material]]
The particle diameter of the particulate carbon material in the heat conductive layer is preferably a volume-based mode diameter of 100 μm or more, more preferably 150 μm or more, and preferably 300 μm or less. If the particle diameter of the particulate carbon material is equal to or more than the above lower limit, the particulate carbon materials are brought into contact with each other in the heat conduction layer to form a good heat transfer path, and thus the heat conduction layer exhibits high thermal conductivity. Because it can. Moreover, if the particle diameter of the particulate carbon material is equal to or less than the above upper limit, flexibility can be imparted to the heat conductive layer.
In the present invention, the “volume-based mode diameter” can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus. In order to measure the volume-based mode diameter of the particulate carbon material contained in the heat conducting layer, specifically, a suspension containing the particulate carbon material is prepared by dissolving the heat conducting layer in a methyl ethyl ketone solvent. obtain. Then, the particle diameter of the particulate carbon material contained in the obtained suspension was measured, and a particle diameter distribution curve with the horizontal axis representing the particle diameter and the vertical axis representing the abundance ratio of the particulate carbon material (volume basis) By obtaining, the particle diameter at the maximum value of the particle diameter distribution curve can be obtained as a volume-based mode diameter.

[[Content ratio of particulate carbon material]]
The content ratio of the particulate carbon material in the carbon material is preferably more than 0% by mass, more preferably 80% by mass or more, further preferably 90% by mass or more, and 99.5%. More preferably, it is more than mass%, can be made into 100 mass% or less, and is preferably 99.9 mass% or less. If the content ratio of the particulate carbon material in the carbon material is equal to or more than the above lower limit, the particulate carbon material is better oriented in the heat conduction layer, and the particulate carbon materials are in contact with each other to provide a good heat transfer path. Form. As a result, high thermal conductivity can be exhibited by the heat conductive layer. Moreover, if the content rate of a particulate carbon material is 99.9 mass% or less, it is because the powder fall of the particulate carbon material from a heat conductive layer can be prevented.

[Fibrous carbon material]
In the heat conductive layer constituting the composite laminate of the present invention, the carbon material preferably contains a fibrous carbon material, and more preferably, the fibrous carbon material is used in combination with the particulate carbon material described above.
Here, the fibrous carbon material is not particularly limited, and for example, carbon nanotubes, vapor-grown carbon fibers, carbon fibers obtained by carbonizing organic fibers, and cut products thereof can be used. . These may be used individually by 1 type and may use 2 or more types together.
And if fibrous carbon material is contained in the heat conductive layer of the composite laminate of the present invention, the heat conductivity of the heat conductive layer can be further improved, and when used in combination with the particulate carbon material, It is also possible to effectively prevent the carbon material from falling off. The reason why powder carbon material can be prevented from falling off by blending the fibrous carbon material is not clear, but the fibrous carbon material forms a three-dimensional network structure, so that the thermal conductivity This is presumably because the particulate carbon material is prevented from being detached while increasing the strength.

  Among the above, as the fibrous carbon material, it is preferable to use a fibrous carbon nanostructure such as a carbon nanotube, and it is more preferable to use a fibrous carbon nanostructure including a carbon nanotube. This is because the use of fibrous carbon nanostructures such as carbon nanotubes can further improve the thermal conductivity and strength of the thermal conductive layer.

[[Fibrous carbon nanostructure containing carbon nanotubes]]
Here, the fibrous carbon nanostructure containing carbon nanotubes that can be suitably used as the fibrous carbon material may be composed only of carbon nanotubes (hereinafter sometimes referred to as “CNT”). Alternatively, a mixture of CNT and a fibrous carbon nanostructure other than CNT may be used.
The CNT in the fibrous carbon nanostructure is not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. Nanotubes are preferable, and single-walled carbon nanotubes are more preferable. This is because if single-walled carbon nanotubes are used, the thermal conductivity and strength of the heat conducting layer can be further improved as compared with the case where multi-walled carbon nanotubes are used.

In addition, the fibrous carbon nanostructure containing CNT has a ratio (3σ / Av) of a value (3σ) obtained by multiplying the standard deviation (σ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20. It is preferable to use a carbon nanostructure of less than 0.60, more preferably a carbon nanostructure with 3σ / Av exceeding 0.25, and a carbon nanostructure with 3σ / Av exceeding 0.50. More preferably. If a fibrous carbon nanostructure containing CNTs with 3σ / Av of more than 0.20 and less than 0.60 is used, the thermal conductivity of the heat conductive layer can be increased.
“Average diameter (Av) of fibrous carbon nanostructure” and “standard deviation of diameter of fibrous carbon nanostructure (σ: sample standard deviation)” are measured using a transmission electron microscope, respectively. It can be determined by measuring the diameter (outer diameter) of 100 randomly selected fibrous carbon nanostructures. And the average diameter (Av) and standard deviation (σ) of the fibrous carbon nanostructure containing CNT are adjusted by changing the manufacturing method and manufacturing conditions of the fibrous carbon nanostructure containing CNT. Alternatively, it may be adjusted by combining a plurality of types of fibrous carbon nanostructures containing CNTs obtained by different production methods.

  Furthermore, the average diameter (Av) of the fibrous carbon nanostructure containing CNT is preferably 0.5 nm or more, more preferably 2.0 nm or more, and preferably 20 nm or less. More preferably, it is as follows. This is because if the average diameter (Av) of the fibrous carbon nanostructure is within the above range, the thermal conductivity and strength of the thermal conductive layer can be increased.

Moreover, it is preferable that the fibrous carbon nanostructure containing CNT has an average length of the structure at the time of synthesis of 100 μm or more and 5000 μm or less. Note that, as the length of the structure at the time of synthesis increases, damage such as breakage or cutting occurs more easily at the time of dispersion. Therefore, the average length of the structure at the time of synthesis is preferably 5000 μm or less.
The aspect ratio (length / diameter) of the fibrous carbon nanostructure is preferably more than 10. The aspect ratio of the fibrous carbon nanostructure was determined by measuring the diameter and length of 100 fibrous carbon nanostructures selected at random using a transmission electron microscope, and the ratio of the diameter to the length (long It can be obtained by calculating an average value of (thickness / diameter).

Furthermore, the BET specific surface area of the fibrous carbon nanostructure containing CNTs is preferably 300 m ² / g or more, more preferably 600 m ² / g or more, and 800 m ² / g or more. More preferably, it is preferably 2500 m ² / g or less, and more preferably 1200 m ² / g or less. This is because if the BET specific surface area of the fibrous carbon nanostructure containing CNTs is 300 m ² / g or more, the thermal conductivity of the heat conductive layer can be increased. Moreover, if the BET specific surface area of the fibrous carbon nanostructure containing CNT is 2500 m ² / g or less, the fibrous carbon nanostructure in the heat conducting layer is suppressed by suppressing aggregation of the fibrous carbon nanostructure. It is because the dispersibility of a body can be improved.
In the present invention, the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.

Furthermore, the fibrous carbon nanostructure containing CNTs is an aggregate oriented in a direction substantially perpendicular to the base material on the base material having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later. Although obtained as a body (aligned aggregate), the mass density of the fibrous carbon nanostructure as the aggregate is preferably 0.002 g / cm ³ or more and 0.2 g / cm ³ or less. If the mass density is 0.2 g / cm ³ or less, since the bonds between the fibrous carbon nanostructures are weakened, the fibrous carbon nanostructures can be uniformly dispersed in the heat conductive layer. Further, if the mass density is 0.002 g / cm ³ or more, the integrity of the fibrous carbon nanostructure can be improved, and it is possible to suppress the variation during the production of the composite laminate of the present invention, so that handling is easy. Become.

  The fibrous carbon nanostructure containing CNTs having the above-described properties can be obtained by, for example, supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on the surface, When synthesizing CNTs by the phase growth method (CVD method), a method of dramatically improving the catalytic activity of the catalyst layer by making a small amount of oxidizing agent (catalyst activation material) present in the system (super growth method) According to International Publication No. 2006/011655). Hereinafter, the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.

  Here, the fibrous carbon nanostructure containing CNT produced by the super-growth method may be composed only of SGCNT, and in addition to SGCNT, other carbon nanostructures such as non-cylindrical carbon nanostructures may be used. Carbon nanostructures may be included.

[[Content ratio of fibrous carbon material]]
And the content rate of the fibrous carbon material in a carbon material can be 0 mass%, It is preferable that it is 0.1 mass% or more, It is preferable that it is less than 100 mass%, and 20 mass% or less. Is more preferably 10% by mass or less, and further preferably 0.5% by mass or less. This is because, if the content ratio of the fibrous carbon material in the carbon material is within the above range, the heat conductivity of the heat conduction layer can be improved and the heat conduction layer can have an appropriate strength.

<Other ingredients>
Optionally, various additives for adjusting the properties of the resin, such as a crosslinking agent, an acid acceptor, and a crosslinking accelerator, and various additives for adjusting the heat conduction performance, etc. with respect to the heat conduction layer. Can be blended. The crosslinking agent is not particularly limited, and examples thereof include a polyol crosslinking agent. As the polyol crosslinking agent, a polyhydroxy aromatic compound can be suitably used. The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane (bisphenol AF). , Resorcinol, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6 -Dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane 4,4'-dihydroxydipheny Sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A, etc. Is mentioned. Of these, bisphenol AF is preferable.
Examples of the acid acceptor include, but are not limited to, magnesium oxide, calcium oxide, zinc oxide, calcium silicate, calcium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite. Among these, magnesium oxide or calcium hydroxide is preferable, and it is more preferable to use these in combination.

As an additive for adjusting the heat conduction performance and the like of the heat conduction layer, a known additive that can be used in forming the heat conductive material can be blended. Examples of such additives include, but are not limited to, silicon carbide, silicon nitride, boron nitride, aluminum nitride, alumina, zinc oxide, magnesium oxide, silica, copper, aluminum, silver, iron, nickel, metal Inorganic fillers such as silicon; plasticizers such as fatty acid esters such as sebacic acid esters; flame retardants such as red phosphorus flame retardants and phosphate ester flame retardants; toughness improving agents such as urethane acrylates; calcium oxide and magnesium oxide Hygroscopic agent; Adhesive strength improver such as silane coupling agent, titanium coupling agent, acid anhydride; Wetting property improver such as nonionic surfactant and fluorine surfactant; Ion trap agent such as inorganic ion exchanger And the like.
Moreover, you may mix | blend a known polymerization initiator in the range which does not impair the objective of this invention.

<Hardness>
In the composite laminate of the present invention, the Asker C hardness at 25 ° C. of the heat conductive layer constituting the composite laminate is preferably 40 or more and 90 or less. The heat conductive layer preferably has an Asker C hardness of 50 or more at 25 ° C., more preferably 60 or more, and preferably 80 or less. If the hardness of a heat conductive layer is more than the said lower limit, the physical strength of a heat conductive layer will increase. Moreover, if the hardness of a heat conductive layer is below the said upper limit, the self-adhesiveness of a heat conductive layer can be improved and the integrity between a heat conductive layer and a coating layer can be improved. At the same time, since the entire composite laminate sheet can be softened, the workpiece is not damaged during thermocompression bonding.

<Thermal conductivity>
Moreover, the heat conductive layer which comprises the composite laminated body of this invention needs that the heat conductivity of the thickness direction is 7.0 W / m * K or more in 25 degreeC. And it is preferable that the heat conductivity in the thickness direction of the composite laminated body of this invention is 8.0 W / m * K or more in 25 degreeC. If thermal conductivity is more than the said minimum, the thermal conductivity of a composite laminated body can fully be improved.

<Thickness>
Furthermore, the heat conductive layer constituting the composite laminate of the present invention preferably has a thickness of 150 μm or more, more preferably 200 μm or more, and is usually 2.0 mm or less and 1.0 mm or less. It is preferable. If the thickness of a composite laminated body is more than the said lower limit, durability of a composite laminated body can be improved. Moreover, if the thickness of a composite laminated body is more than the said lower limit and below an upper limit, it can be compatible with the flexibility and intensity | strength of a composite laminated body.

<Coating layer>
The coating layer is a transfer-preventing layer for suppressing the component contained in the heat conductive layer from being transferred to the workpiece when the composite laminate of the present invention is brought into contact with the workpiece in a high heat state. It is. For example, the coating layer can be a film formed of a heat resistant resin or a release resin. And the coating layer may contain arbitrary additives. The content ratio of the heat resistant resin or the release resin in the coating layer is preferably 50% by mass or more, more preferably 75% by mass or more, and 90% by mass with respect to the total mass of the coating layer. % Or more is more preferable, and 100% by mass is particularly preferable.

[Heat resistant resin]
The heat resistant resin that can form the coating layer is not particularly limited, and examples thereof include polyimide resin, polyether sulfide resin, polyethylene naphthalate resin, polyamideimide resin, and polybenzoxazole resin. Among these, imide resins such as polyimide resins and polyamideimide resins are preferable, and polyimide resins are more preferable.

[Releasable resin]
"Releasable resin" is a resin that can exhibit releasability. Examples of the releasable resin include a fluororesin. The fluororesin is not particularly limited. For example, tetrafluoroethylene-perfluoro (alkyl vinyl ether) resin (PFA resin), polytetrafluoroethylene (PTFE) resin, tetrafluoroethylene-hexafluoropropylene (FEP) resin. Etc. Among these, PFA resin is preferable.

  Among these, from the viewpoint of improving transfer resistance and self-adhesive properties, an imide resin is preferable as the resin for the coating layer.

  The glass transition temperature (Tg) of the resin capable of forming the coating layer is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and usually 600 ° C. or lower and 500 ° C. or lower. preferable.

[Thickness of coating layer]
The thickness of the coating layer is not particularly limited and is preferably 5 μm or more and 20 μm or less. When the thickness of the coating layer is not less than the above lower limit, the transfer resistance of the composite laminate can be improved. Moreover, if the thickness of a coating layer is below the said upper limit, the heat conductivity of a composite laminated body can be improved further.

<Shape of composite laminate>
The shape of the composite laminate of the present invention is not particularly limited as long as it includes the heat conductive layer satisfying the above-mentioned predetermined properties and the coating layer, and for example, any shape suitable for use such as a sheet shape and a cylindrical shape. It can be a shape. More specifically, the composite laminate of the present invention that can be suitably used as a thermocompression bonding sheet may have a sheet shape.
In particular, in the composite laminate of the present invention, it is preferable that the heat conductive layer has a structure in which strips containing a resin and a carbon material are joined in parallel. Such a structure is not particularly limited, and can be suitably formed through a manufacturing method described in detail below. In addition, in the manufacturing method described in detail below, an element called “pre-heat conductive layer” may correspond to the “strip”. And in this pre heat conductive layer, ie, a strip, since a carbon material orientates in the thickness direction, a heat conductive layer is excellent in the heat conductivity of the thickness direction.

<Composite laminate manufacturing method>
And a composite laminated body is not specifically limited, For example, the composite material containing resin and a carbon material is pressurized and shape | molded in a sheet form, and the process (pre heat conductive layer shaping | molding process) of obtaining a pre heat conductive layer, , Laminating a plurality of pre-heat conductive layers in the thickness direction, or folding or winding the pre-heat conductive layer to obtain a laminate (laminate formation step), and laminating the obtained laminate A step of slicing at an angle of 45 ° or less with respect to the direction to obtain a sheet-like heat conduction layer (slicing step), and a step of obtaining a composite laminate by laminating a coating layer on the obtained heat conduction layer ( Sheet stacking step).

[Pre-heat conductive layer forming process]
In the pre heat conductive layer forming step, a pre heat conductive layer can be obtained by pressurizing a composite material containing a resin and a carbon material, and optionally further containing an additive, into a sheet shape. Note that the composite material including the resin and the carbon material may be prepared and prepared by any method, or a commercially available product may be purchased and prepared.

[[Preparation of composite materials]]
When preparing a composite material, it can prepare by stirring and mixing resin and a carbon material, and arbitrary additives. And as a resin, a carbon material, and an additive, what was mentioned above as a resin, a carbon material, an additive, and other component which can be contained in the composite laminated body of this invention can be used.

  Incidentally, when the resin contained in the composite laminate is a crosslinkable resin, a pre-heat conductive layer may be formed using a composite material containing the crosslinkable resin, or a crosslinkable resin and a crosslinker. A pre-heat conductive layer may be formed using a composite material containing, and a cross-linkable resin may be contained in the composite laminate by cross-linking a cross-linkable resin after the pre-heat conductive layer forming step.

[[Composite molding]]
And after defoaming and crushing arbitrarily, the composite material prepared as mentioned above can be pressurized and formed into a sheet. Here, the composite material is not particularly limited as long as it is a molding method in which pressure is applied, and can be molded into a sheet using a known molding method such as press molding, rolling molding, or extrusion molding.

  And in the pre-heat conduction layer formed by pressing the composite material into a sheet shape, it is presumed that the carbon materials are arranged mainly in the in-plane direction, and in particular the heat conductivity in the in-plane direction of the pre-heat conduction layer is improved. The Further, when the carbon material contains a fibrous carbon material, the fibrous carbon material is oriented in the pre-heat conductive layer, so that it is presumed that the thermal conductivity of the pre-heat conductive layer is further improved.

  In addition, the thickness of a pre heat conductive layer is not specifically limited, For example, it can be 0.05 mm or more and 2 mm or less. Further, from the viewpoint of further improving the thermal conductivity of the composite laminate, the thickness of the pre-heat conductive layer is preferably 0.10 mm or more, and preferably 0.80 mm or less.

[Laminated body forming step]
In the laminated body forming step, a plurality of pre heat conductive layers obtained in the pre heat conductive layer forming step may be laminated in the thickness direction, or the pre heat conductive layer may be folded or wound to obtain a laminate. it can. Here, in the laminated body obtained in the laminated body forming step, the adhesive force between the surfaces of the pre-thermal conductive layers is usually sufficient by the pressure when laminating the pre-thermal conductive layers and the pressure when folding or winding. Is obtained. Alternatively, when the composite material contains a cross-linked resin, a plurality of pre-heat conductive layers can be bonded to each other by interposing a common double-sided tape or adhesive between adjacent pre-heat conductive layers. .

  In the laminate obtained by laminating, folding or winding the pre-heat conductive layer, carbon materials such as particulate carbon material and / or fibrous carbon material are arranged in a direction substantially orthogonal to the laminating direction. It is guessed.

[Slicing process]
In the slicing step, the laminated body obtained in the laminated body forming step can be sliced at an angle of 45 ° or less with respect to the laminating direction to obtain a composite laminated body composed of sliced pieces of the laminated body.

[Sheet lamination process]
In the sheet laminating step, a sheet-like coating layer is laminated on the obtained sheet-like heat conductive layer to obtain a sheet-like composite laminate. As a method of bonding the heat conductive layer and the coating layer to each other, for example, a sheet-shaped coating layer is placed on the sheet-shaped heat conductive layer, and a load is applied from above the sheet-shaped coating layer. The method of pressing with respect to a heat conductive layer is mentioned. By maintaining such a load-loading state, for example, for 1 hour or more and 48 hours or less, the heat conductive layer and the coating layer can be bonded to each other.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
In the examples and comparative examples, the glass transition temperature of the coating layer, the thermal conductivity of the heat conductive layer and the composite laminate, the Asker C hardness of the heat conductive layer, the anti-transfer characteristics of the composite laminate, and the self of the heat conductive layer The tackiness was measured or evaluated according to the following methods.

<Glass transition temperature (Tg)>
The glass transition temperature Tg of the resin forming the coating layer used in Examples and Comparative Examples was measured according to JIS K7121.

<Thermal conductivity>
A resin material thermal resistance tester (trade name “C47108” manufactured by Hitachi Technology & Service Co., Ltd.) was used to measure the thermal resistance values of the heat conductive layers and composite laminates produced in the examples and comparative examples. Each of the heat conductive layer and the composite laminate was cut into 1 cm squares as test specimens. The thermal resistance value (m ² K / W) when a pressure of 0.05 MPa was applied to the specimen was measured. The temperature of the test body at the time of measurement was 50 ° C. It shows that it is excellent in thermal conductivity, and is excellent in the heat dissipation characteristic at the time of interposing between a heat generating body and a heat radiator as a heat resistance value, so that it is small. And the thickness (m) of the test body was divided by the value of the obtained thermal resistance value, and the value of thermal low efficiency (W / m · K) was calculated.

<Asker C hardness>
The Asker C hardness of the heat conductive layer was measured in an environment at a temperature of 25 ° C. using a hardness meter in accordance with the Asker C method of the Japan Rubber Association Standard (SRIS 0101).
Specifically, the heat conductive layers obtained in the examples and comparative examples were cut into a size of 30 mm long × 50 mm wide × 1.0 mm thick, and 30 sheets were stacked. And the test body was obtained by leaving the laminated | stacked heat conductive layer for 48 hours or more in the thermostat kept at the temperature of 25 degreeC. Next, the height of the damper was adjusted so that the pointer became 95 to 98, and the specimen and the damper were made to collide. And the Asker C hardness of the test body 60 seconds after the collision is measured twice using a hardness meter (product name “ASKER CL-150LJ” manufactured by Kobunshi Keiki Co., Ltd.), and the average value of the measurement results is adopted. did. A smaller Asker C hardness indicates higher flexibility.

<Self-adhesive>
The composite laminates produced in the examples and comparative examples were cut into 3 cm squares and used as test specimens. A double-sided tape was affixed to the surface of the test body on the heat conductive layer side, and was fixed to the approximate center of the upper surface of a 6 cm × 6 cm glass plate via the double-sided tape. The edge part of the glass plate was supported, and it hold | maintained for 10 second in the state turned upside down so that a coating layer might become the lower side, and visually observed how a coating layer peeled from a composite laminated body.
A: The state in which the coating layer is adhered to the specimen is maintained even after 10 seconds from upside down. B: The specimen is covered with its own weight within 1 second to 10 seconds after upside down. Peel from.
C: The coating layer peels off from the specimen under its own weight in less than 1 second after turning upside down.

<Transfer resistance>
Using the sheet-like composite laminates obtained in Examples and Comparative Examples as thermocompression-bonding sheets, the transfer resistance characteristics when the synthetic resin materials A and B were thermocompression-bonded were evaluated. Synthetic resin materials A and B were both made of polypropylene, and each was molded into a star shape (size that fits in a circle with a diameter of 6 cm). Next, 0.20 g of an adhesive made of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin) is applied between the synthetic resin materials A and B, and the synthetic resin material A and the synthetic resin material B are bonded. It laminated | stacked through the agent. At this time, the adhesive was in a solid state at room temperature, and the synthetic resin materials A and B were not bonded by the adhesive.
Subsequently, the obtained laminate of synthetic resin material A / adhesive / synthetic resin material B was fixed to an ultrasonic welder (product name “HiQ VARIO” manufactured by Herman Ultrasonic) via the composite laminate. . The ultrasonic welder was equipped with an ultrasonic oscillator and a fixture as a heating device. Specifically, there is a pedestal with a metal jig as a fixture on the lower side of the ultrasonic welder, and a horn that generates ultrasonic waves is attached as a heating device on the upper side of the ultrasonic welder. The laminate is fixed between these pedestals and the horn so that the synthetic resin material A is on the upper side (side facing the horn) and the synthetic resin material B is on the lower side (side fixed to the pedestal). did. Moreover, in the case of fixation, the composite laminated body obtained by the Example and the comparative example was interposed between the synthetic resin material B side and the base among laminated bodies. In other words, from above, a pedestal having a horn (ultrasonic oscillator) as a heating device / synthetic resin material A / adhesive / synthetic resin material B / composite laminate as a thermocompression bonding sheet / metal jig as a fixture In this order, the laminate was fixed to an ultrasonic welder.
Subsequently, the synthetic resin material A and B are thermocompression-bonded by irradiating the synthetic resin material A side with ultrasonic waves from the upper horn and transferring heat generated from the vibration energy of the ultrasonic waves to dissolve the adhesive. It was. Here, the synthetic resin material A and the horn were in contact with each other during irradiation with ultrasonic waves. The conditions for thermocompression bonding by ultrasonic irradiation were as follows: press pressure: 180 N / mm ² , ultrasonic frequency: 30 kHz, ultrasonic treatment time: about 5 seconds, output: 1800 W.
Then, after the synthetic resin materials A and B are thermally welded as described above, the laminate is removed from the ultrasonic welder, and the surface of the laminate on the side of the synthetic resin material B, that is, the base via the composite laminate. The surface state of the fixed side was visually observed, and the surface dirtiness of the synthetic resin material was evaluated according to the following criteria. The smaller the surface contamination of the synthetic resin material, the higher the transfer resistance of the composite laminate.
Here, in this evaluation standard, “dirt” is a component of a film or resin attached on the surface of the synthetic resin material B that is fixed to the pedestal via the composite laminate. The “dirt size” is defined as a diameter when a circumscribed circle is set for the outline of the attached portion. The “dirt” includes those having a size that is difficult to confirm visually, and such a “dirt” can be relatively easily observed using a microscope such as an electron microscope. . The “dirt” here is physically adhered to the synthetic resin and is different from dust that can be easily removed by air spray or the like. On the other hand, it can be easily removed by wiping with a cloth or the like.
A: Dirt cannot be confirmed even with a microscope B: Dirt size is 20 μm or more and 500 μm or less C: Dirt exceeding 500 μm exists

Example 1
<Preparation of fibrous carbon material>
400 mg of SGCNT (average fiber diameter: 3.5 nm, BET specific surface area: 800 m ² / g, single-walled CNT, 3σ / Av: 0.28) synthesized according to the method described in International Publication No. 2006/011655 The mixture was mixed in 2 L of methyl ethyl ketone as a solvent, and stirred for 2 minutes with a homogenizer to obtain a crude dispersion. Next, using a wet jet mill (product name “JN-20”, manufactured by Joko Co., Ltd.), the obtained coarse dispersion is passed through a 0.5 mm flow path of the wet jet mill at a pressure of 100 MPa for two cycles. Then, the fibrous carbon nanostructure was dispersed in methyl ethyl ketone. And the dispersion liquid of solid content concentration 0.20 mass% was obtained. Thereafter, the dispersion obtained above was filtered under reduced pressure using Kiriyama filter paper (No. 5A) to obtain a sheet-like easily dispersible aggregate as a fibrous carbon material.

<Pre-heat conductive layer molding process>
[Preparation of composite materials]
0.50 parts by mass of an easily dispersible aggregate of carbon nanostructures as a fibrous carbon material and expanded graphite as a particulate carbon material (trade name “EC-100”, manufactured by Ito Graphite Industries Co., Ltd., average) 50 parts by mass of a particle diameter: 190 μm) and 100 parts by mass of a normal temperature liquid thermoplastic fluororesin (made by Daikin Industries, Ltd., trade name “DAIEL G-101”) as a resin , Trade name “ACM-5LVT type”, capacity: 5 L), and heated to 80 ° C. and mixed for 30 minutes. The composition obtained by mixing was put into a wonder crush mill (trade name “D3V-10” manufactured by Osaka Chemical Co., Ltd.) and crushed for 1 minute. The volume fraction of expanded graphite as the particulate carbon material in all the composite materials was 28% by volume.
[Pre-heat conductive layer forming process]
Next, 50 g of the pulverized composite material is sandwiched between 50 μm thick PET films (protective film) subjected to sandblast treatment, a roll gap of 550 μm, a roll temperature of 50 ° C., a roll linear pressure of 50 kg / cm, and a roll speed of 1 m / min. Roll forming was performed under the conditions to obtain a pre-heat conductive layer having a thickness of 0.5 mm.
<Laminated body formation process>
The obtained pre-heat conductive layer was cut into 15 cm × 15 cm × 0.5 mm, 120 layers were laminated in the thickness direction, and pressed at 0.1 MPa for 3 minutes at 120 ° C. to obtain a laminate having a thickness of about 6 cm.
<Slicing process>
Then, using a slicer for woodworking (manufactured by Marunaka Co., Ltd., trade name “Super-finished plane board super mechanism S”) while pressing the laminated section of the laminated body of the pre-heat conducting layer with a pressure of 0.3 MPa. Then, it is sliced at an angle of 0 degrees with respect to the lamination direction (in other words, sliced in the normal direction of the main surface of the laminated pre-heat conduction layer), and the heat conduction layer 15 cm long × 6 cm wide × 150 μm thick Got. As the knife for the woodworking slicer, a knife having a single blade of 0.2 mm higher than the slide surface and a blade angle of 21 ° was used.
<Sheet lamination process>
For the obtained heat conductive layer, a polyimide film (Kapton 50H, thickness: 12.5 μm, Tg: 410 ° C., manufactured by Toray DuPont Co., Ltd.) as a coating layer is 15 cm long × 6 cm wide × 15 μm thick. And laminated on the heat conductive layer, and a weight of 100 g with the same area was placed thereon and pressed for 24 hours to obtain a composite laminate.

(Example 2)
In preparation of the composite material, a bisphenol AF crosslinking agent (Tokyo Chemical Industry Co., Ltd.) as a crosslinking agent with respect to 100 parts by mass of a normal temperature liquid thermoplastic fluororesin (made by Daikin Industries, Ltd., trade name “DAIEL G-101”) as a resin. 1 part by weight of VC-50), 6 parts by weight of calcium hydroxide (Omi Chemical Co., Ltd .: Caldic 2000) as an acid acceptor, magnesium oxide as an acid acceptor (Kyowa Chemical Industry) 3 parts by weight of Kyowamag 150) was added, and the mixture was stirred using Hobart under the same conditions as in Example 1. Except for this point, a heat conductive layer and a composite laminate were produced in the same manner as in Example 1, and various measurements and evaluations were performed. The results are shown in Table 1.

(Example 3)
In preparing the composite material, instead of 100 parts by mass of a normal temperature liquid thermoplastic fluororesin (made by Daikin Industries, Ltd., trade name “DAIEL G-101”) as a resin, a two-component curable liquid silicone resin (made by Momentive) 100 parts by mass of TSE-3062A solution and B solution) were added at a mass ratio of 1: 1. Further, the amount of graphite as the particulate carbon material was increased to 90 parts by mass, and the volume fraction of expanded graphite in all the composite materials was adjusted to be 28% by volume as in Example 1. Except for these points, a heat conductive layer and a composite laminate were produced in the same manner as in Example 1, and various measurements and evaluations were performed. The results are shown in Table 1.

Example 4
Instead of the polyimide film, a film made of PFA fluororesin (manufactured by Daikin Industries, “Neofuron PFA film”, thickness: 15 μm, Tg: 100 ° C.) was used as the coating layer. Except for this point, a heat conductive layer and a composite laminate were produced in the same manner as in Example 1, and various measurements and evaluations were performed. The results are shown in Table 1.

(Example 5)
Instead of the polyimide film, a film made of PFA fluororesin (manufactured by Daikin Industries, “Neofuron PFA film”, thickness: 15 μm, melt Tg: 100 ° C.) was used as the coating layer. Except for this point, a heat conductive layer and a composite laminate were produced in the same manner as in Example 3, and various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, the heat conductive layer which does not have a coating layer was obtained without performing the sheet laminating step. Various measurements and evaluations were performed using the obtained heat conductive layer as it was. The results are shown in Table 1.

(Comparative Example 2)
In preparing the composite material, a heat conductive layer and a composite laminate were produced in the same manner as in Example 3 except that the particulate carbon material was not blended, and various measurements and evaluations were performed. The results are shown in Table 1.

(Comparative Example 3)
The same process as in Example 3 was performed until the pre-heat conductive layer forming step. And the sheet | seat lamination process was implemented with respect to the pre thermal conductive layer, without implementing a laminated body formation process and a slice process, and the laminated body by which a coating layer was laminated | stacked on the pre thermal conductive layer was obtained. The thermal conductivity, Asker C hardness, and self-adhesive properties of the pre-thermal conductor, and the thermal conductivity and anti-transfer properties of the laminate were measured according to the above methods. The results are shown in Table 1.

  In the table, “PI” indicates polyimide, and “PFA” indicates tetrafluoroethylene-perfluoro (alkyl vinyl ether).

From Table 1, the composite laminated body of Examples 1-5 which has resin and a carbon material, and has a heat conductive layer whose thermal conductivity is more than a predetermined value, and a coating layer has sufficient heat conductivity, It can be seen that the transfer resistance is high.
Moreover, the thermal conductivity of the comparative example 1 which is not provided with a coating layer, the comparative example 2 where the thermal conductivity of the thermal conductive layer is low, and the pre thermal conductive layer corresponding to the thermal conductive layer is less than 7.0 W / m · K. In Comparative Example 3, it can be seen that the thermal conductivity and anti-transfer characteristics of the composite laminate cannot be achieved.

  ADVANTAGE OF THE INVENTION According to this invention, while having sufficient thermal conductivity, the composite laminated body and composite laminated sheet which can suppress the transcription | transfer to the workpiece surface are provided.

Claims (6)

A heat conductive layer including a resin and a carbon material and having a thermal conductivity in the thickness direction of 7.0 W / m · K or more;
A coating layer;
A composite laminate comprising:   The composite laminate according to claim 1, wherein the coating layer contains a resin having a glass transition temperature of 80 ° C. or higher.   The composite laminate according to claim 1, wherein the coating layer contains a fluororesin or an imide resin.   The composite laminated body in any one of Claims 1-3 whose said resin contained in the said heat conductive layer is a fluororesin or a silicone resin.   The composite laminated body in any one of Claims 1-3 whose said resin contained in the said heat conductive layer is a thermoplastic fluororesin which is a liquid under normal temperature normal pressure.   A composite laminate sheet comprising the composite laminate according to claim 1.