JP2008049607A - Heat-conductive laminate with bonded thin film of electrical insulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-conductive laminate which consists of a molding composed of a resin composition containing carbon fibers of a high degree of graphitization with excellent heat conductivity and has electrical insulating properties. <P>SOLUTION: The laminate which meets electrical insulation requirements while retaining high heat conductivity is obtained by preparing pitch-based carbon fibers of a high heat conductivity, serving as a heat conductive material, with the size, surface geometry and fine structures of the graphite crystals controlled, by dispersing the carbon fibers appropriately with a matrix of e.g. a thermosetting or a thermoplastic resin to form a composite material so as to obtain a molding of e.g. an electrically insulating material and by making an electrical insulating thin film of silica, alumina, etc. overlie the surface or cross-section of the composite material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a technique for improving a molded article composed of thermally conductive partially graphitized carbon fiber, and in particular,
The present invention relates to a thermally conductive material made of carbon fiber having electrical insulation. More specifically, a pitch-based carbon fiber is used as a raw material, and this is graphitized to improve thermal conductivity. Further, a composition in which the carbon fiber is a matrix of a thermosetting resin and / or a thermoplastic resin. In addition, the present invention relates to a molding material / laminated material obtained by depositing and laminating a thin layer having electrical insulation properties to impart electrical insulation properties.

  Carbon fiber originates from the structure of its raw material, and is a linear carbon fiber made from a chain (linear) polymer, such as cellulose fiber or polyacrylonitrile (PAN), and a plane made from a cyclic condensation polymer. It can be classified as a carbon fiber. Conventionally, chain carbon fiber uses the characteristics that strength and elastic modulus are remarkably higher than ordinary synthetic polymers, and is used for aerospace and space equipment, construction and civil engineering materials, industrial robots, sports and leisure equipment. It is used in a wide range of fields. In particular, PAN-based carbon fibers are often used for applications that utilize their mechanical strength, and pitch-based carbon fibers are often used for fields that use elastic modulus.

  The carbon fiber is obtained by making the above-mentioned raw material into a fiber in a spinning process, then subjecting it to an infusibilizing treatment, and further applying a crystallization treatment at a high temperature. By this crystallization heat treatment, the carbon fiber partially becomes graphite crystals. Compared to carbon fibers derived from linear polymers, planar carbon fibers made from pitch are easier to graphitize, have a higher degree of crystallinity, and a larger crystal size.

  By the way, in recent years, in the field of communication and information industries, heat generation by a high-speed CPU and heat generation by Joule heat of an electronic circuit are being recognized as serious problems. In order to solve these problems, it is pointed out that it is necessary to consider a technique for efficiently processing heat, so-called thermal management.

  In order to realize this thermal management, it is common to use a metal material having high thermal conductivity such as metal, metal oxide, metal nitride, metal oxynitride, and alloy. A typical example is metal die casting. However, in order to fabricate a housing of an electrical component having a complicated shape, the above-mentioned partially graphitized carbon fiber material is used as a heat conductive material, and a heat-resistant material serving as a matrix is blended with the composite material. It becomes a preferable aspect to use as. However, the thermal conductivity of the synthetic resin that can be applied to the matrix is about 1/100 or less that of the graphite fiber, and as a result, a large amount of carbon fiber needs to be blended as a composite material.

  However, the addition of a large amount of carbon fiber filler in the composite material leads to instability of moldability and impairs practicality as a molded product. For such reasons, there has been a demand for a highly thermally conductive carbon fiber filler in which consideration has been given to a shape that can efficiently exhibit thermal conductivity.

  Carbon fibers have higher thermal conductivity than other synthetic polymers, but further improvements in thermal conductivity are being studied for thermal management applications. However, the thermal conductivity of commercially available PAN-based carbon fibers is usually smaller than 200 W / (m · K). This is because PAN-based carbon fibers are so-called “non-graphitizable” carbon fibers, and it is very difficult to increase the degree of graphitization responsible for heat conduction. On the other hand, pitch-based carbon fibers are called “easily graphitized” carbon fibers, and can have a higher degree of graphitization than PAN-based carbon fibers, so that high thermal conductivity is easily achieved. Therefore, there is an expectation that a high thermal conductivity carbon fiber filler can be obtained after high thermal conductivity can be expressed and the shape as a carbon fiber aggregate is studied.

  However, since it is difficult to directly process the carbon fiber alone into the heat conductive member, it is necessary to use a special means. Therefore, like a metallic filler or the like, it is required to form a composite material of some matrix and carbon fiber, to form a molded body, and to improve the thermal conductivity of the molded body.

  And in order for a molded object to achieve predetermined | prescribed heat conduction, the carbon fiber filler which mainly bears heat conduction needs to form the network in three dimensions. For example, in the case of spherical fillers of uniform size, it can be seen that the filler network in the molded body depends on the dispersion state but assumes a percolation behavior when uniform dispersion is assumed. Thus, in order to obtain sufficient thermal conductivity and electrical conductivity as a molded article, it is necessary to add a certain amount of filler. However, when forming a molded body, a thickening action or a non-uniform dispersion state occurs between the medium and the filler, and it may be difficult to disperse the medium and the filler at a predetermined concentration. Therefore, it is desired that the composition be effective even if the filler addition amount is small.

  In view of such a background, studies have been made to give fillers three-dimensional crosslinking. For example, Patent Document 1 discloses an attempt to transport a heat flow by forming a metal network. However, it is considered that a very high level of technology is required for dispersion into the matrix. Patent Document 2 discloses that alloying causes the matrix and the filler to melt simultaneously, and as a result, high thermal conductivity is achieved while maintaining formability.

However, the addition of a metal material whose specific gravity is larger than that of the resin increases the specific gravity of the resin composition, and uses such as a heat sink for an integrated circuit and a CPU of an electric computer, etc. to discuss weight reduction on the order of 1 g. I have to say that it is disadvantageous.
Furthermore, depending on the application, there are applications in which electrical insulation is required while maintaining thermal conductivity. Since the partially graphitized carbon fiber is remarkably rich not only in heat conductivity but also in electrical conductivity, it is necessary to reliably cut off the conductive performance by an insulating material.

Japanese Patent Laid-Open No. 6-196684 International Publication No. 03/029352 Pamphlet

  It is necessary to obtain a resin composition having high thermal conductivity and at the same time having electrical insulation. In order to achieve this problem, a carbon fiber with a high graphite component, which is a material with high thermal conductivity, is demanded. Furthermore, sufficient thermal conductivity is exhibited in the final use state, and electrical insulation is also achieved. It is necessary to be sure.

  The inventors of the present invention aim to improve thermal conductivity in a final molded body such as a heat radiating member. For example, the main component is pitch-based carbon fiber having high thermal conductivity as a thermal conductive material. After controlling the size, surface shape and microstructure, further dispersing and compositing with the matrix appropriately, and then laminating an electrically insulating thin film on the surface and cross-section, it maintains electrical conductivity while maintaining high thermal conductivity. The inventors have found that the insulating properties can be satisfied and have reached the present invention.

  That is, the first embodiment of the present invention maintains the state in which the insulating property can be expressed as it is as the electrically insulating thin film appears on the surface or cross section as the composite material for molding of claim 1. And a heat conductive laminated material obtained by laminating an electrically insulating thin film on a molded body composed of a carbon fiber aggregate and a matrix.

  The invention of claim 2 which is the second embodiment of the present invention is to ensure electrical insulation in a molded product obtained by molding the above-mentioned composite material, and has a surface or cross section of the molded body. It is a heat conductive laminated material formed by coating or bonding an electrically insulating thin film made of an inorganic polymer or an organic polymer. According to a third aspect of the present invention, which is a third embodiment of the present invention, the above-mentioned electrically insulating thin film contains at least one selected from the group consisting of silica, alumina, zirconia, titania and boron nitride. Conductive laminate. Since these have insulating properties and thermal conductivity, they function effectively as electrically insulating thin films. According to a fourth aspect of the present invention, which is a fourth embodiment of the present invention, the above-mentioned electrically insulating thin film is a film made of an organic polymer having a thickness of 1 to 100 μm. These have the characteristics that the strength of the electrically insulating thin film is maintained by using a thin organic polymer for the electrically insulating thin film and the thermal conductivity is not impaired. In addition, the organic polymer film is made of polyimides, polyamides, polyesters, and polycarbonates, which are excellent in terms of heat resistance and handling properties.

  As a preferred embodiment of the present invention, carbon fiber having high thermal conductivity and high graphitization degree should be selected, cyclic hydrocarbon having condensed heterocyclic ring, that is, pitch-based carbon raw material should be used, The carbon fiber aggregate accumulated in a mat shape obtained through the spinning process is made of, for example, a pitch-based carbon fiber filler whose observation surface by a scanning electron microscope is substantially flat, and an average fiber diameter observed by an optical microscope ) Is in the range of 1 μm to 20 μm, the end face of the carbon fiber filler is closed, the average fiber length is in the range of 5 μm to 1000 μm, and the aspect ratio of the fiber length to the fiber diameter is in the range of 1 to 100 It is clearly shown that those having a CV in the range of 5 to 18 exhibit an optimum graphitization rate.

  When the graphitization rate is high, the true density of the carbon fiber is in the range of 1.5 to 2.2 g / cc, and the thermal conductivity in the fiber axis direction is 300 W / (m · K) or more. The crystal size in the thickness direction of the hexagonal mesh surface is 10 nm or more, and the crystal size in the growth direction of the hexagonal mesh surface is also grown to 8 nm or more.

  The invention described in claim 10 is composed of carbon fiber aggregates having different fiber diameters and / or fiber lengths in pitch-based carbon fibers, and exhibits a high carbon fiber filling rate when this aggregate and a matrix are combined. Thus, it has been found that a molded article having a composition having high thermal conductivity can be obtained.

  In the production of long fibers and short fibers, in order to obtain a carbon fiber sheet having two types of fiber lengths that are reasonably long and short while suppressing production costs, the same pitch raw material is used, and the pitch fibers are spun under almost the same conditions. To do. The pitch fiber is collected on the wire mesh belt without changing the conditions such as the spinneret, spinning temperature, discharge rate per hour, heated gas temperature / spout speed from the slit, and the spout position. After adjusting the basis weight, lightly adhere with a binder, add a rolling press, infusibilize, and further calcinate, and then shorten the pitch fiber using a milling device. obtain.

Subsequently, it is blended with the pitch-based carbon fiber comprising the remaining long fibers previously collected on the wire mesh belt to obtain a flat mixed fiber sheet. When adjusting to this sheet, it is possible to apply a wet papermaking method in which water-swellable organic polymers such as polyvinyl alcohol (PVA) fibers are partially used instead of binders, and use short air and long fibers by utilizing the amount of air. A dry papermaking method in which fibers are mixed with a thermoplastic resin instead of a binder and fused together can be applied.
After that, if necessary, a carbon fiber aggregate for a composite material that can be mixed with a matrix is obtained through various steps such as infusibilization, firing treatment, and graphitization treatment.

The carbon fiber sheet having two kinds of long and short fiber lengths has an average diameter of single fibers in the range of 1 to 20 μm, the average fiber length of single fibers is 2000 μm (2.0 mm) or less, and the average fiber length relative to the average diameter Ratio, that is, a pitch-based carbon fiber (short fiber A) having an aspect ratio of 1 to 100, and a carbon fiber having a fiber average diameter of 2 to 40 μm and a single fiber having an average fiber length of 5 to 150 mm ( Long fibers B) are mixed so that the weight ratio of short fibers A to long fibers B is 1 to 99 to 99 to 1.
The crystallite size in the growth direction of the hexagonal network surface of the pitch-based carbon fiber short fibers A in this carbon fiber sheet is 5 nm or more, the thickness is 0.05 to 5 mm, and the porosity is 50 to 90 volumes. %.

  A composite molding material is obtained by blending a matrix made of a resin or the like into the carbon fiber sheet having the end face closed as described above or the carbon fiber sheet having two kinds of long and short fiber lengths. The carbon fiber aggregate of the present invention is characterized by containing the carbon fiber material in a volume fraction of 3 to 60% by volume with respect to the matrix.

  The matrix is a thermoplastic resin and / or a thermosetting resin. For example, the thermoplastic resin may be polycarbonates, polyethylene terephthalates, polyethylene 2,6 naphthalates, nylons, polypropylenes, polyethylenes, polyepoxyether ketones. At least one resin selected from the group of polyether ether ketones and polyphenylene sulfides. For example, the thermosetting resin is selected from the group of epoxies, acrylics, urethanes, silicones, and phenols. At least one resin. And the heat conductivity of the composite material in the state shape | molded in the flat form or its molded object is 2 W / (m * K) or more.

The composite material of the present invention is formed into a molded product by at least one molding means selected from the group of injection molding, press molding, calendar molding, roll molding, extrusion molding, cast molding, and blow molding. Can be molded.
Furthermore, when the composite molded product formed by molding the carbon fiber composite material does not maintain electrical insulation, an insulation treatment can be performed. As already described, this insulation treatment is performed by a processing method of forming an electrically insulating thin film made of an inorganic polymer or an organic polymer, or an electrically insulating thin film made of a metal oxide or ceramic on the surface or cross section of a molded product. Achieved.
Examples of suitable applications include a heat radiating member for electronic parts, a radio wave shielding plate, a heat exchanger, and the like, which are mainly made of the composite molded product of the present invention.

  The composite molded product of the present invention is processed into a heat radiating member of an electronic component as a main material, and can be used for a heat radiating case such as a heat sink for an integrated circuit or a CPU of an electric computer. Moreover, the carbon fiber derived from the pitch-based material can be applied to a radio wave shielding plate by being excellent in radio wave shielding performance in a frequency band of several GHz.

  Furthermore, depending on the application, there are applications in which electrical insulation is required while maintaining thermal conductivity. Since the graphitized carbon fiber has a high electrical conductivity, the conductive portion can be reliably cut off by the insulating material.

  The pitch-based carbon fiber filler that can be used in the present invention has a specific shape and is controlled in size, thereby imparting high thermal conductivity to the composite molded body while suppressing an increase in the viscosity of the matrix. Therefore, a composite molding material having good moldability and high thermal conductivity can be obtained.

Next, embodiments of the present invention will be described in detail.
Examples of the raw material for pitch-based carbon fibers that can be used in the present invention include condensed polycyclic hydrocarbon compounds such as naphthalene and phenanthrene, condensed heterocyclic compounds such as petroleum-based pitch and coal-based pitch, and the like. In particular, condensed polycyclic hydrocarbon compounds such as naphthalene and phenanthrene are preferred. In particular, an optically anisotropic pitch, that is, a mesophase pitch is preferable. These may be used singly or in appropriate combination of two or more, but the use of mesophase pitch alone can increase the graphitization rate in the graphitization treatment, and consequently The thermal conductivity of the carbon fiber can be improved, which is a preferred embodiment.

The softening point of the raw material pitch can be determined by the Mettler method, and is preferably in the range of 230 ° C. or higher and 340 ° C. or lower. If the softening point is lower than 230 ° C., fusion between fibers or large heat shrinkage occurs during infusibilization. If the temperature is higher than 340 ° C., the pitch is thermally decomposed in the spinning process, which tends to make the spinning molding difficult. Further, under high temperature spinning conditions, gas components are generated, bubbles are generated in the spun yarn, causing strength deterioration, and yarn breakage is likely to occur.
The raw material pitch is spun by a melt blow method, and then becomes pitch-based carbon fiber having a relatively short fiber length by various processes of infusibilization, firing, milling, sieving, and graphitization.

Each process will be described below.
In the present invention, there is no particular restriction on the shape of the spinning nozzle when spinning the pitch fiber that is the raw material of the pitch-based carbon fiber. However, the nozzle hole length / hole diameter ratio is preferably smaller than 3, more preferably about 1.5.
There are no particular restrictions on the nozzle temperature during spinning, and there is no problem as long as the temperature can maintain a stable spinning state. When the viscosity of the raw material pitch is in an appropriate range, the spinning state may be stabilized, that is, the temperature at which the spinning pitch has a viscosity of 1 to 30 Pa · S, preferably 8 to 16 Pa · S.

The pitch fibers drawn out from the nozzle holes can be made by a melt-blowing method in which the fibers are shortened by blowing a gas having a linear velocity of 100 to 10000 m per minute heated to 100 to 370 ° C. in the vicinity of the thinning point. As the gas to be blown, air, nitrogen, argon or the like can be used, but air is preferable from the viewpoint of cost performance.
The pitch fibers are collected on a wire mesh belt to form a continuous mat, and are further cross-wrapped to form a web having a predetermined basis weight (weight per unit area).

  The web made of pitch fibers thus obtained can be infusibilized by a known method. The infusibilization temperature is 200 to 320 ° C. For infusibilization, heat treatment is performed at a temperature of 200 to 320 ° C. for a certain time using air or a mixed gas obtained by adding ozone, nitrogen dioxide, nitrogen, oxygen, iodine or bromine to air. Considering safety and convenience, it is desirable to carry out in air.

The infusible pitch fiber is subsequently fired in a temperature range of 600 to 1000 ° C. in a vacuum or in an inert gas such as nitrogen, argon or krypton. Usually, the calcination is performed using nitrogen which is inexpensive at normal pressure.
The web made of infusibilized and fired pitch fibers is further milled and sieved in order to further shorten the fibers and to obtain a predetermined fiber length. For milling, a pulverizer or cutting machine such as a Victory mill, a jet mill, or a high-speed rotary mill is used. In order to perform milling efficiently, a method of cutting fibers in a direction perpendicular to the fiber axis by rotating a rotor to which blades are attached at high speed is appropriate.

The average fiber length of the fibers produced by milling is controlled by adjusting the rotational speed of the rotor, the angle of the blade, and the like. Furthermore, it divides into 10-100 micrometers by a sieve, More preferably, it is 15-50 micrometers. Alternatively, it is divided into 100 to 1000 μm, more preferably 100 to 400 μm. Such adjustment of the average fiber length can be made by combining the coarseness of the sieve.
The above-mentioned milled and sieved fibers are heated to 2300-3500 ° C. and graphitized to obtain the final pitch-based carbon short fibers. Graphitization is performed in a non-oxidizing atmosphere in an Atchison furnace or the like.

  Next, the shape of the pitch-based carbon short fiber filler of the present invention will be described. When the shape of the filler end face is observed with a transmission electron microscope, the pitch-based carbon fiber of the present invention has a structure in which the graphene sheet is closed. When the end face of the filler is closed as a graphene sheet, generation of extra functional groups and localization of electrons due to shape do not occur, so the concentration of impurities such as water can be reduced, For example, the affinity with expanded graphite can be further increased, which is preferable. In particular, the present invention can be applied to a filler having a fiber length shorter than 1 mm, but a structure in which the graphene sheet is closed is particularly preferable because the ratio of the end face to the filler surface area is increased.

  Note that the graphene sheet is closed means that the end of the graphene sheet itself constituting the carbon fiber is not exposed at the end of the carbon fiber, the graphite layer is curved in a substantially U shape, and the curved portion is the end of the carbon fiber. It is in the state exposed to the part.

The pitch-based carbon fiber filler used in the present invention has a substantially flat observation surface with a scanning electron microscope. Here, “substantially flat” means that the surface does not have severe unevenness like a fibril structure, and when there is intense unevenness on the surface of the filler, the surface area increases upon kneading with the matrix resin. It is desirable that the surface irregularities be as small as possible because it causes an increase in the viscosity associated with the above and lowers the moldability.
The pitch-based carbon fiber filler described above can be easily obtained by performing graphitization after milling.

  The average fiber diameter of the pitch-based carbon fiber filler of the present invention observed with an optical microscope is desirably 1 to 20 μm, and more desirably 7 to 12 μm. When the fiber diameter is larger than 20 μm, adjacent fibers are likely to be fused in the infusibilization process. When the fiber diameter is less than 1 μm, the surface area per weight of the pitch-based carbon fiber filler is increased, and the fiber surface is substantially increased. Even if it is flat, the formability is lowered in the same manner as the fiber having irregularities on the surface, and it is inappropriate in practice. Moreover, the ratio with respect to the diameter of fiber diameter dispersion | distribution which is dispersion | distribution of the fiber diameter observed with the optical microscope has the preferable range of 3 to 20%.

  The average fiber length of the pitch-based carbon fiber filler of the present invention is 10 to 1000 μm. The fiber length has an optimum value depending on the application, but in the case where the filler exhibits a secondary effect, the range of 100 to 700 μm is preferable. More preferably, it is the range of 100-500 micrometers. On the other hand, when the filler is used for preparing a heat transfer path, that is, for a heat dissipation member, the fiber length is preferably in the range of 10 to 500 μm. More preferably, it is the range of 10-300 micrometers. When the fiber length is shorter than 10 μm, it is difficult to maintain the fiber shape. On the other hand, when the fiber length exceeds 500 μm, the bulk density becomes small and mixing with the matrix component becomes difficult. In addition, it is preferable that the aspect ratio (L1 / D1) of a fiber is the range of 1-100.

  L1 / D1 depends on the average fiber length. On the other hand, when L1 / D1 is smaller than 1, powder falling in the final molded product becomes remarkable. On the other hand, if L1 / D1 exceeds 100, the percentage of fibers that breaks increases, making it difficult to express original performance. In a more preferred embodiment, when the average fiber length is 10 to 100 μm, the aspect ratio is about 1.5 to 10, and when the average fiber length is 300 to 500 μm, the aspect ratio is 30 to 50.

  The fiber diameter dispersion (S1) CV with respect to the average fiber diameter (D1) is preferably 5 to 18. Carbon fibers having a CV as small as 18 or more have a large variation in fiber diameter, so that the dispersibility in the matrix is poor and the thermal conductivity is not stable. On the other hand, when the CV is 5 or less, the dispersion of the fiber diameter is small and the dispersion is good, but since the dispersion is very good, the contact between the fibers cannot be expected so much and the thermal conductivity becomes low.

In the present invention, the true density of the pitch-based carbon fiber filler strongly depends on the graphitization temperature, but is preferably in the range of 1.5 to 2.2 g / cc. More preferably, it is 1.8-2.2 g / cc. The thermal conductivity in the fiber axis direction of the pitch-based carbon fiber is 300 W / (m · K) or more, and more preferably 400 W / (m · K) or more.
In addition, the pitch-based carbon fiber filler has a hexagonal mesh surface with a crystal size in the thickness direction of 10 nm or more, and a hexagonal mesh surface in the growth direction with a crystal size of 8 nm or more.

  The crystal size corresponds to graphitization in both the thickness direction of the hexagonal mesh surface and the growth direction of the hexagonal mesh surface, and in order to develop thermophysical properties, crystal grains of a certain size or larger are required. is necessary. The crystallite size derived from the thickness direction of the hexagonal mesh surface and the crystallite size in the growth direction of the hexagonal mesh surface can be obtained by an X-ray diffraction method. The measurement method was the concentration method, and the Gakushin method was used as the analysis method. The crystal size in the thickness direction of the hexagonal mesh plane is obtained using diffraction lines from the (002) plane, and the crystal size in the growth direction of the hexagonal mesh plane is obtained using diffraction lines from the (110) plane, respectively. Can do.

In the present invention, a pitch-based carbon fiber filler and a matrix are mixed to produce a carbon fiber composite material. At this time, the pitch-based carbon short fiber filler is added in a volume fraction of 3 to 60% with respect to the matrix. On the other hand, when the addition amount is less than 3% by volume, it is difficult to sufficiently develop the thermal conductivity. On the other hand, it is often difficult in practice to add more than 60% by volume of pitch-based carbon fiber filler to the matrix.
The matrix contains either a thermoplastic resin or a thermosetting resin. Further, as the matrix, a thermoplastic resin and a thermosetting resin can be appropriately mixed and used in order to develop desired physical properties in the composite molded product.

  The thermoplastic resin is at least selected from the group consisting of polycarbonates, polyethylene terephthalates, polyethylene 2,6 naphthalates, nylons, polypropylenes, polyethylenes, polyepoxy ether ketones, polyether ether ketones, polyphenylene sulfides. One type can be selected.

  Specifically, polyethylene-polypropylene, ethylene-α-olefin copolymer such as ethylene-propylene copolymer, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, Polyvinyl alcohol, polyacetal, fluororesin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene ether (PPE) ) Resin, modified PPE resin, aliphatic polyamide, aromatic polyamide, polyimide, polyamideimide, polymethacrylic acid (polymethacrylic acid such as polymethylmethacrylate) Ester), polyacrylic acids, polycarbonate, polyphenylene sulfide, polysulfone, polyether sulfone, polyether nitrile, polyether ketone, polyketone, liquid crystal polymer, ionomer and the like. And as a matrix, 1 type may be used individually from these, 2 or more types may be used in combination suitably, and the polymer alloy which consists of 2 or more types of polymeric materials may be used.

  Examples of the thermosetting resin include epoxies, acrylics, urethanes, silicones, phenols, imides, thermosetting modified PPEs, thermosetting PPEs, and the like. Or two or more types may be used in appropriate combination.

  The composite molded product of the present invention is produced by mixing a pitch-based carbon fiber filler and a matrix. During mixing, a kneader, a mixer, a blender, a roll, an extruder, a milling machine, a self-revolving stirrer For example, a mixing device or a kneading device is preferably used. The composite molded body can be molded by a molding method such as an injection molding method, a press molding method, a calendar molding method, a roll molding method, an extrusion manufacturing method, a casting molding method, or a blow molding method.

  Molding conditions vary depending on the matrix and molding technique means, but in the case of a thermoplastic resin, molding is carried out with the temperature raised from the melt viscosity of the resin. In the case where the matrix is a thermosetting resin, a method of heating to a curing temperature of the resin in an appropriate mold can be exemplified.

The carbon fiber composite material can also be obtained by processing the matrix resin into a shape such as a planar shape in advance and press-molding it in a state of being laminated with a pitch-based carbon fiber sheet in which carbon fibers are dispersed.
Also in this case, at the time of vacuum press molding, molding in a vacuum state for the purpose of suppressing generation of voids is the same as in the first method.

In the present invention, electrical insulation is ensured by the electrically insulating thin film. The electrical insulation shown here means that the surface resistance is 10 ⁶ Ω / □ or more. The surface resistance can be measured with a commercially available four-terminal surface resistance meter.

  The electrically insulating thin film can be made from an inorganic polymer or an organic polymer. The inorganic polymer or the organic polymer is not particularly limited, and specifically, silicone can be used as the inorganic polymer, and polyamides, polyimides, polycarbonates, polyesters, and the like can be used as the organic polymer. Basically, many of the above-described electrically insulating thin films have poor thermal conductivity. Then, the heat conductivity of a heat conductive molded object can be effectively maintained by containing the heat conductive substance which has insulation in an electrically insulating thin film, and keeping heat conductivity. Although there is no limitation in particular in a heat conductive substance, Specifically, a silica, an alumina, a zirconia, a titania, and boron nitride can be used.

  An electrically insulating thin film made of an organic polymer can easily impart insulation to a carbon fiber composite material if it is previously formed into a film shape. The film made of the organic polymer is preferably thin, and the film thickness is desirably 1 to 100 μm or less. When the film thickness is thinner than 1 μm, the mechanical strength of the film is very small and the handling property is inferior, making it difficult to bond the insulating thin film to the carbon fiber composite material. On the other hand, when the film thickness is thicker than 100 μm, the film is basically inferior in thermal conductivity, so that the thermal conductivity of the thermally conductive molded body may be impaired.

Although there is no limitation in particular in the organic polymer used for a film, the organic polymer shown above can be used.
Although there is no limitation in particular as a method of laminating the film in the above to a carbon fiber composite material, specifically, a method of applying an adhesive or the like to at least one surface of a film or a carbon fiber composite material, and a film and carbon fiber There is a method of pressing a composite material with a press molding machine or the like.

Other methods for forming an electrically insulating thin film on the surface of the carbon fiber composite material include electroless plating, electrolytic plating, vacuum deposition, sputtering or ion plating, chemical vapor deposition, and coating on the surface of the molded product. There is a technique of coating an electrically insulating metal oxide or ceramic by a mechanochemical method in which immersion or fine particles are mechanically fixed.
The pitch-based carbon fiber sheet and / or short carbon fiber may be surface-treated and then a sizing agent may be added thereto.

  As the surface treatment method, the surface may be modified by oxidation treatment such as electrolytic oxidation, or by treatment with a coupling agent or sizing agent. Also, by means such as electroless plating, electrolytic plating, physical vapor deposition such as vacuum deposition, sputtering, ion plating, chemical vapor deposition, painting, dipping, and mechanochemical methods for mechanically fixing fine particles. A metal or ceramic coated on the surface may be used.

  The sizing agent is added to the pitch-based carbon fiber sheet and / or short carbon fiber in an amount of 0.1 to 15% by weight, preferably 0.1 to 7.5% by weight. Any commonly used sizing agent can be used. Specifically, an epoxy compound, a water-soluble polyamide compound, a saturated polyester, an unsaturated polyester, vinyl acetate, water, alcohol, glycol alone or a mixture thereof may be used. it can. Such surface treatment is effective because it increases the bulk density. However, since excessive sizing agent adhesion results in thermal resistance, it is adjusted according to the required physical properties.

  When the composite molded product of the present invention is molded into a flat plate shape and the thermal conductivity is measured, it shows a thermal conductivity of 2 W / (m · K) or more. The thermal conductivity of 2 W / (m · K) is about one digit (about 10 times) higher than that of the polymer material used as the matrix.

  The composite molded product of the present invention can be used as a heat sink for electronic components by utilizing its high thermal conductivity. In addition, since high thermal conductivity can be obtained by increasing the amount of pitch-based carbon fiber filler added, automobiles that require relatively high heat resistance in electronic components and industrial power modules that require large currents It can be suitably used for a connector or the like. More specifically, it can be used for a heat sink, a semiconductor package component, a heat sink, a heat spreader, a die pad, a printed wiring board, a cooling fan component, a housing, and the like. It can also be used as a part of a heat exchanger. Can be used for heat pipes. Furthermore, the radio wave shielding property of the pitch-based carbon fiber filler is utilized, and it can be suitably used particularly as a radio wave shielding member in the GHz band.

Examples are shown below, but the present invention is not limited thereto.
(1) Average fiber diameter and fiber diameter dispersion of pitch-based carbon short fiber filler:
The pitch-based carbon fiber filler that had undergone graphitization was determined by photographing 10 fields of view at 400 times under an optical microscope.
(2) Average fiber length of pitch-based carbon short fiber filler:
The pitch-based short carbon fiber filler that had undergone graphitization was determined by photographing 10 visual fields under an optical microscope. The magnification was appropriately adjusted according to the yarn length.
(3) True density of pitch-based carbon short fiber filler:
It calculated | required using the specific gravity method.
(4) Crystal size:
Obtained by X-ray diffraction, the crystal size in the thickness direction of the hexagonal mesh surface is obtained using the diffraction line from the (002) plane, and the crystal size in the growth direction of the hexagonal mesh surface is the diffraction line from the (110) plane. Obtained using. In addition, the request was made in accordance with the Gakushin Law.
(5) Thermal conductivity of pitch-based carbon short fiber filler:
The resistivity of pitch-based short carbon fibers after graphitization prepared under the same conditions except for the pulverization step is measured, and the relationship between the thermal conductivity and electrical resistivity disclosed in JP-A-11-117143 is expressed. It calculated | required from following formula (1).
[Equation 1]
K = 1272.4 / ER-49.4 (1)
Here, K represents the thermal conductivity W / (m · K) of the pitch-based carbon fiber after graphitization, and ER represents the electrical specific resistance μΩm of the same pitch-based carbon fiber.
(6) Thermal conductivity of thermally conductive laminate:
Measured with QTM-500 manufactured by Kyoto Electronics.
(7) Insulating property of the molded body Measured with a Loresta EP from Dia Instruments.

[Experimental Example 1]
A pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material. The optical anisotropy ratio was 100%, and the softening point was 283 ° C. A spinneret having a circular hole with a diameter of 0.2 mm was used, heated air was ejected from the slit at a linear velocity of 5000 m / min, and the melt pitch was pulled to produce a pitch fiber having an average fiber diameter of 15 μm. The spun pitch-based fibers were collected on a belt to form a mat, and then a web made of pitch-based fibers having a basis weight of 320 g / m ^{2 by} cross wrapping.

  The web was infusibilized by increasing the temperature from 175 ° C. to 280 ° C. in air at an average temperature increase rate of 7 ° C./min. The infusible web was fired at 800 ° C. in a nitrogen atmosphere, and then milled, and sieved to a short fiber filler having an average fiber length of 25 μm. Then, it graphitized by heat-processing at 3000 degreeC with the electric furnace made into the non-oxidizing atmosphere, and it was set as the pitch-type carbon fiber filler. The average fiber diameter was 9.7 μm. CV was 14%. The true density was 2.05 g / cc.

The image was observed with a transmission electron microscope at a magnification of 1,000,000 times and magnified on a photograph at 4 million times. It was confirmed that the graphene sheet was closed at the end face of the pitch-based carbon short fiber filler. Further, the surface of the pitch-based carbon short fiber filler, which was observed with a scanning electron microscope at a magnification of 4000 times, was smooth with no large irregularities.
The crystal size in the thickness direction of the hexagonal network surface determined by the X-ray diffraction method was 15 nm. The crystal size in the growth direction of the hexagonal network surface was 20 nm.

A single yarn was extracted from a graphitized web prepared by the same process up to firing and not milled, and heat-treated at 3000 ° C. in an electric furnace in a non-oxidizing atmosphere, and the electrical resistivity was measured. It was 2.4 μΩm. The thermal conductivity obtained using the following formula (1) was 480 W / (m · K).
[Equation 2]
K = 1272.4 / ER-49.4 (1)

[Experiment 2]
A pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material. The optical anisotropy ratio was 100%, and the softening point was 283 ° C. Using a spinneret with a circular cross-sectional hole having a diameter of 0.2 mm, heated air was ejected from the slit at a linear velocity of 6000 m / min, and the melt pitch was pulled to produce pitch fibers having an average fiber diameter of 11 μm. The spun short fibers were collected on a belt to form a mat, and then a web made of pitch fibers having a basis weight of 280 g / m ^{2 by} cross wrapping.

  The web was infusibilized by increasing the temperature from 175 ° C. to 280 ° C. in air at an average temperature increase rate of 7 ° C./min. The infusible web was fired at 800 ° C. in a nitrogen atmosphere and then milled and sieved to a short fiber filler having an average fiber length of 30 μm. Then, it graphitized by heat-processing at 3000 degreeC with the electric furnace made into the non-oxidizing atmosphere, and it was set as the pitch-type carbon short fiber filler. The average fiber diameter was 8.1 μm. CV was 16%. The true density was 2.0 g / cc. The image was observed with a transmission electron microscope at a magnification of 1,000,000 times and magnified on a photograph at 4 million times. The graphene sheet was closed on the end face of the pitch-based carbon short fiber filler. Further, the surface of the pitch-based carbon short fiber filler observed with a scanning electron microscope at a magnification of 4000 times was smooth with no large irregularities.

The crystal size in the thickness direction of the hexagonal network surface determined by the X-ray diffraction method was 17 nm. The crystal size in the growth direction of the hexagonal network surface was 25 nm.
A single yarn was extracted from a graphitized web prepared by the same process up to firing and not milled, and heat-treated at 3000 ° C. in an electric furnace in a non-oxidizing atmosphere, and the electrical resistivity was measured. 2.2 μΩm. The thermal conductivity obtained using the above formula (1) was 530 W / (m · K).

[Experiment 3]
By adjusting the opening of sieving after milling with the same web as in Experimental Example 1, a pitch-based carbon short fiber filler having an average fiber length of 350 μm was obtained.
The average fiber diameter was 9.9 μm. CV was 16%. The true density was 2.05 g / cc. The image was observed with a transmission electron microscope at a magnification of 1,000,000 times and magnified on a photograph at 4 million times. The graphene sheet was closed on the end face of the pitch-based carbon short fiber filler. Further, the surface of the pitch-based carbon short fiber filler, which was observed with a scanning electron microscope at a magnification of 4000 times, was smooth without any large unevenness.

The crystal size in the thickness direction of the hexagonal network surface determined by the X-ray diffraction method was 14 nm. The crystal size in the growth direction of the hexagonal network surface was 19 nm.
The thermal conductivity is the same as that of Experimental Example 1 because the graphitized material is used as it is as the web before milling.

[Experimental Example 4]
By adjusting the opening of sieving after milling with the same web as in Experimental Example 2, a pitch-based carbon short fiber filler having an average fiber length of 400 μm was obtained.
The average fiber diameter was 7.9 μm. CV was 15%. The true density was 2.0 g / cc. The image was observed with a transmission electron microscope at a magnification of 1,000,000 times and magnified on a photograph at 4 million times. The graphene sheet was closed on the end face of the pitch-based carbon short fiber filler. Further, the surface of the pitch-based carbon short fiber filler, which was observed with a scanning electron microscope at a magnification of 4000 times, was smooth with no large irregularities.

The crystal size in the thickness direction of the hexagonal network surface determined by the X-ray diffraction method was 16 nm. The crystal size in the growth direction of the hexagonal network surface was 24 nm.
The thermal conductivity is the same as that in Experimental Example 2 because the graphitized material is used as it is as the web before milling.

[Experimental Example 5]
The process up to milling was the same as in Experimental Example 1, and graphitized at 2300 ° C. in an electric furnace in a non-oxidizing atmosphere to obtain a pitch-based carbon short fiber filler. The average fiber length was 30 μm.
The average fiber diameter was 10.6 μm. CV was 13%. The true density was 1.8 g / cc. The image was observed with a transmission electron microscope at a magnification of 1,000,000 times and magnified on a photograph at 4 million times. The graphene sheet was closed on the end face of the pitch-based carbon short fiber filler. Further, the surface of the pitch-based carbon short fiber filler, which was observed with a scanning electron microscope at a magnification of 4000 times, was smooth with no large irregularities.

The crystal size in the thickness direction of the hexagonal network surface determined by the X-ray diffraction method was 11 nm. The crystal size in the growth direction of the hexagonal network surface was 10 nm.
A single yarn was extracted from a graphitized web prepared by the same process up to firing and not milled, and heat-treated at 2300 ° C. in an electric furnace in a non-oxidizing atmosphere, and the electrical resistivity was measured. It was 3.4 μΩm. The thermal conductivity obtained using the above formula (1) was 320 W / (m · K).

[Experimental Example 6]
The production of short fibers is as follows.
In order to obtain a carbon fiber sheet having reasonably two types of long and short fiber lengths while suppressing production cost, pitch fibers are spun under substantially the same conditions using the same pitch raw material. The pitch fiber is collected on the wire mesh belt without changing the conditions such as the spinneret, spinning temperature, discharge rate per hour, heated gas temperature / spout speed from the slit, and spout position, and if necessary, cross-wrapping. After adjusting the basis weight, lightly adhering with a binder, adding a rolling press, infusibilizing, further firing, and then shortening this pitch fiber using a milling device, short fiber A Get.

  Next, a mixed fiber sheet of long fibers and short fibers was prepared. A flat mixed fiber sheet is obtained by blending with pitch meter carbon fibers made of long fibers B previously collected on a wire mesh belt. When adjusting to this sheet, apply a wet papermaking method in which a water-swellable organic polymer such as polyvinyl alcohol (PVA) fiber is partially used in place of a binder, or using short amount of air A dry papermaking method in which long fibers are mixed and fused with a thermoplastic resin instead of a binder can be applied. After that, if necessary, a carbon fiber aggregate for a composite material that can be mixed with a matrix is obtained through various steps such as infusibilization, firing treatment, and graphitization treatment.

A pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material. The main raw material had an optical anisotropy ratio of 100% and a softening point of 285 ° C. A spinneret having a diameter of 0.2 mm was used, heated air was ejected from the slit at a linear velocity of 5000 m / min, and the melt pitch was pulled to spin pitch-based long fibers having an average diameter of 11 μm. The spun fibers were collected on a belt to form a mat, further cross-wrapped, and shaped into a pitch fiber sheet having a three-dimensional random shape with a basis weight of 250 g / m ² .

  A part of this pitch fiber sheet is subjected to the following treatment to obtain short carbon fibers. That is, this pitch fiber sheet was infusibilized by raising the temperature from 170 ° C. to 300 ° C. at an average temperature raising rate of 5 ° C./min. The infusible pitch fiber sheet was fired at 900 ° C., then shortened with a pulverizer, and then fired at 3000 ° C. to obtain pitch-based carbon short fibers. The average diameter (D1) of the pitch-based carbon short fibers was 10 μm, and the ratio of the fiber diameter dispersion to D1 (CV1) was 18%. The average fiber length (L1) was 0.5 mm. The crystallite size in the growth direction of the hexagonal network surface was 46 nm. The thermal conductivity in the fiber axis direction was 590 W / (m · K). The true density of the pitch-based carbon short fibers was 2.1 g / cc.

  In order to make the remaining pitch fiber sheet into carbon long fibers, the infusible pitch fiber sheet was fired and graphitized at 3000 ° C. to obtain a pitch carbon fiber sheet having a three-dimensional random shape. The pitch fiber diameter constituting the pitch-based carbon fiber sheet was 11 μm on average, the variation rate CV was 13%, and the fiber length was 100 mm on average. The crystallite size was 46 nm, and the thermal conductivity was 595 W / (m · K).

Next, 50 parts by weight of pulverized short carbon fibers were dispersed in a manner of dry blending with respect to 100 parts by weight of the pitch-based carbon fiber sheet and mixed to obtain a pitch-based carbon fiber reinforcing material.
Next, a maleic acid-modified polypropylene film manufactured by Sanyo Kasei Co., Ltd. was used as the matrix resin, and the pitch-based carbon fiber reinforcement was set to 40% as the volume ratio of the molded body. In addition, press molding was performed so that the inner diameter was 1 mm with a 650 mm inner die. The thermal conductivity of the molded carbon fiber composite material was measured and found to be 5.5 W / (m · K).

[Experimental Example 7]
A pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material. This main raw material had an optical anisotropy ratio of 100% and a softening point of 285 ° C. A spinneret having a diameter of 0.2 mm was used, heated air was ejected from the slit at a linear velocity of 4800 m / min, and the pitch pitch fiber having an average diameter of 12 μm was spun by pulling the melt pitch. The spun fibers were collected on a belt to form a mat, and further, a pitch fiber mat having a three-dimensional random shape with a basis weight of 250 g / m ² was obtained by cross wrapping.

  This pitch fiber mat was heated in the air from 170 ° C. to 300 ° C. under an average temperature rising rate of 5 ° C./min for infusibilization treatment. The infusible pitch fiber mat was fired and graphitized at 3000 ° C. to obtain a pitch-based carbon fiber sheet having a three-dimensional random shape. The fiber diameter of the pitch-based carbon fibers constituting the pitch-based carbon fiber sheet was 10 μm on average, and the diameter variation rate CV was 19%. The fiber length was 150 mm on average. The crystallite size was 47 nm and the thermal conductivity was 610 W / (m · K).

The pitch fiber mat having been subjected to the infusibilization treatment was fired at 700 ° C., then shortened with a pulverizer, and then further fired and graphitized at 3000 ° C. to obtain carbon fibers. The carbon fiber had an average fiber diameter of 10 μm and a diameter variation rate CV of 19%. The average fiber length of these short fibers was 0.2 mm.
Next, a polycarbonate resin manufactured by Teijin Chemicals Ltd. is used as a matrix resin, 20 parts by weight of carbon fiber is melt-kneaded with 100 parts by weight of the polycarbonate resin using a twin screw extruder equipped with a film forming die, and then a film A molded product was obtained.

  Furthermore, a pitch-based carbon fiber sheet used as a pitch-based carbon fiber reinforcing material using a polycarbonate film containing carbon short fibers B obtained by the above method, a polycarbonate film manufactured by Teijin Chemicals Limited and a pitch-based carbon fiber reinforcing material The weight ratio of carbon fibers to short fibers is 100 parts by weight: 50 parts by weight, and the carbon fiber reinforcement is set to 45% as the volume ratio of the molded body. Using a 650 mm mold, press molding was performed so that the thickness became 1 mm. The thermal conductivity of the molded carbon fiber composite material was measured and found to be 6.1 W / (m · K).

Bonding of electrical insulating film [Example 1]
The electrical insulating thin film shown below was bonded to the carbon fiber composites obtained in Experimental Examples 6 and 7 by hot pressing (200 ° C.), and the electrical insulating properties and thermal conductivity were observed. Display these results.

The electrically insulating thin film was obtained by the following method.
Aramika: Using Teijin Advanced Film (film thickness 12μm)

[Example 2]
The following electrical insulating thin films were formed on the carbon fiber composite materials obtained in Experimental Examples 6 and 7 by coating and post-treatment. The electrical insulation and thermal conductivity were observed.

The electrically insulating thin film was obtained by the following method.
Silicone: Two-component curable silicone (SE1821 manufactured by Toray Dow Silicone) was cast on a carbon fiber composite material to a thickness of 20 μm with a doctor blade. Then, the silicon | silicone was hardened by processing at 140 degreeC for 1 hour, and the thin film was formed.
Polyamide thin film: Conex (manufactured by Teijin) was dissolved in dichloromethane, cast on a heat conductive laminate to a thickness of 20 μm, and the solvent was removed at 80 ° C.
Silicone + boron nitride thin film: Two-component curable silicone (SE1821 manufactured by Toray Dow Silicone) was mixed with boron nitride so as to be 50% by weight, cast on a thermally conductive laminate to a thickness of 20 μm, and 140 The silicone was cured by treatment at 1 ° C. for 1 hour to form a thin film.

[Experiment 3]
A thin film of silica having a thickness of 20 angstroms was formed by sputtering the carbon fiber composite materials obtained in Experimental Examples 6 and 7 in a vacuum. The electrical insulation and thermal conductivity were observed.

[Comparative Example 1]
The electrical conductivity of the carbon fiber composites obtained in Experimental Examples 6 and 7 was measured. Experimental Example 6 was 1.8Ω / □, and Experimental Example 7 was 0.9Ω / □.

Claims (24)

  A heat-conductive laminated material obtained by laminating an electrically insulating thin film on a molded body composed of a carbon fiber aggregate and a matrix.   2. The thermal conductivity according to claim 1, wherein an electrically insulating thin film made of an inorganic polymer or an organic polymer is applied or bonded to the surface or cross section of a molded body made of a composition of a carbon fiber aggregate and a matrix. Laminated material.   The heat conductive laminated material according to claim 1 or 2, wherein the electrically insulating thin film according to claim 2 contains at least one selected from the group consisting of silica, alumina, zirconia, titania and boron nitride. .   The heat conductive laminated material according to any one of claims 1 to 3, wherein the electrically insulating thin film according to claim 2 or 3 is a film made of an organic polymer having a thickness of 1 to 100 µm.   The heat conduction according to any one of claims 1 to 4, wherein the organic polymer film according to claim 4 is made of at least one resin selected from the group of polyimides, polyamides, polyesters, and polycarbonates. Laminated material.   The heat conductive laminated material of Claim 1 formed by coating the electrically insulating thin film which consists of a metal oxide or ceramics on the surface or cross section of the molded object which consists of a composition of a carbon fiber aggregate and a matrix.   The carbon fiber aggregate according to any one of claims 1 to 6 comprises a pitch-based carbon fiber filler, an average fiber diameter (D1) observed with an optical microscope is in a range of 1 µm to 20 µm, and an average fiber length (L1). Is in the range of 5 μm to 1000 μm, the aspect ratio of L1 to D1 is in the range of 1 to 100, and the ratio (CV1) of fiber diameter dispersion (S1) to D1 is in the range of 5 to 18. The heat conductive laminated material of any one of Claims 1-6.   8. The heat conduction including the pitch-based carbon fiber filler according to claim 7, wherein the true density is in the range of 1.5 to 2.2 g / cc, and the thermal conductivity in the fiber axis direction is 300 W / (m · K) or more. Laminated material.   The pitch-based carbon fiber filler according to claim 7 or 8, wherein the crystal size derived from the thickness direction of the hexagonal network surface is 10 nm or more, and the crystallite size derived from the growth direction of the hexagonal network surface is 8 nm or more. Thermally conductive laminate including   The heat conductive laminate comprising the pitch-based carbon fiber filler according to claim 7, wherein the carbon fiber aggregate is a three-dimensional random mat obtained by a melt blow method.   The carbon fiber aggregate is composed of pitch-based carbon fibers having different fiber diameters and / or fiber lengths, and when combined with a matrix, a molded body having a composition having a high carbon fiber filling rate is obtained. The heat conductive laminated material as described in.   The thermally conductive laminated member according to any one of claims 1 to 6, comprising a thermoplastic resin and / or a thermosetting resin as a matrix.   The thermoplastic resin used as the matrix is selected from the group consisting of polycarbonates, polyethylene terephthalates, polyethylene 2,6 naphthalates, nylons, polypropylenes, polyethylenes, polyepoxy ether ketones, polyether ether ketones, and polyphenylene sulfides. The thermally conductive laminate according to claim 12, comprising at least one kind of resin.   The heat conductive laminated member according to claim 12, comprising at least one resin selected from the group of epoxies, acrylics, urethanes, silicones, and phenols as a thermosetting resin serving as a matrix.   A method for producing a thermally conductive laminate, comprising a step of molding a composite molding material containing a carbon fiber aggregate and a matrix to obtain a molded product, and then providing an electric insulating layer on the surface of the molded product.   The thermal conductive laminate material according to any one of claims 12 to 14, wherein the thermal conductivity of the thermally conductive laminate material in a state of being shaped into a flat plate is at least 2 W / (m · K). Method.   The surface of the molded product formed by molding a heat conductive carbon fiber composite material including a carbon fiber aggregate and a matrix is electrically insulated by electroless plating, electrolytic plating, vacuum deposition, sputtering or ion plating. The method for processing a carbon fiber composite molded article according to claim 1 or 6, wherein metal oxide or ceramic is vapor-deposited.   Electricity is generated by chemical vapor deposition, painting, dipping, or mechanochemical method of mechanically fixing fine particles to the surface of a molded product formed by molding a thermally conductive carbon fiber composite material containing a carbon fiber aggregate and a matrix. The method for processing a carbon fiber composite molded article according to claim 1 or 6, wherein an insulating metal oxide or ceramic is coated.   The processing of the heat conductive laminated material according to claim 1 or 2, wherein an electrically insulating thin film of an inorganic polymer or an organic polymer is coated on the surface of a molded body composed of a carbon fiber aggregate and a matrix. Law.   The processing method of the heat conductive laminated material of Claims 1-4 which bonds the film which consists of an organic polymer to the surface of at least one of the molded object which consists of a carbon fiber aggregate and a matrix.   The composite molding material according to any one of claims 12 to 14, at least selected from the group consisting of an injection molding method, a press molding method, a calendar molding method, a roll molding method, an extrusion molding method, a casting molding method, and a blow molding method. A method for producing a composite molded article formed by one type of forming means.   The heat radiating member for electronic components which uses the composite molding in any one of Claims 12-14 as a main material.   The electromagnetic wave shielding board which uses the composite molding in any one of Claims 12-14 as a main material.   The heat exchanger which uses the composite molded product in any one of Claims 12-14 as a main material.