JP2012251144A - Composite resin composition and molding excellent in heat dissipation property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin composition which is more excellent in molding processability, lightweight properties, and heat radiation properties than a metal material and more excellent in thermal conductivity and mechanical strength than a resin material.SOLUTION: The composite resin composition includes (A) heat conductive fibers and (B) resin as constituent materials. In the composite resin composition, thermal conductivity in a planar direction measured based on the laser flash method in a molded article obtained by molding the resin composition is 5 W/mK or more, the thermal conductivity in the thickness direction is a half or less the thermal conductivity in the planar direction, the bending strength measured based on JIS K 6911 is ≥80 MPa, and the bending elastic modulus is ≥8 GPa, the specific gravity is ≥1 and ≤5 measured based on JIS K 6911, and the linear expansion coefficient in the planar direction is ≥0.1 ppm/°C and ≤50 ppm/°C. The molding excellent in heat conductivity is produced by using the composite resin composition.

Description

  The present invention relates to a composite resin composition and a molded article excellent in heat dissipation.

  In recent years, in the field of electronics and the automobile industry, research on heat dissipation and weight reduction of materials has been actively conducted for energy saving and downsizing of products.

  A metal material is mentioned as a typical material excellent in heat dissipation. Metallic materials have malleability and ductility, and are excellent in electrical conductivity, thermal conductivity, heat resistance, rigidity, and other strengths, so they can be used for building materials such as structural materials and electronic components such as electrical and electronic parts. Widely used in industrial applications. However, on the other hand, since a molding method such as melting or cutting is used, the load on the environment due to the large energy for melting the metal, the high cost due to the relatively poor machinability, the weight due to the large specific gravity, etc. There are also disadvantages such as increase, generation of rust due to oxidation, low vibration absorption, and inability to maintain shape due to plastic deformation.

  On the other hand, since the specific gravity is small, the resin material is a very effective material when attempting to reduce the weight. Typical characteristics of the resin are its low specific gravity, excellent insulation, elasticity, vibration absorption, corrosion and chemical resistance, and good workability, so it is mass-produced industrially. Moreover, it is one of the features that it is excellent in thermal radiation compared with a metal material. However, compared to metals, the strength and heat resistance are weak, the thermal conductivity is remarkably low, and it is easy to be charged with static electricity. Therefore, it is difficult to simply use a resin that is inexpensive and has good workability instead of a metal material.

Therefore, it has been attempted to develop a material having heat dissipation characteristics while being lightweight by filling a resin material with a highly heat conductive filler.
By filling the voids of the metal fiber non-woven fabric with a resin mixed with a heat conductive filler, the study of suppressing the disadvantages while utilizing the characteristics of each metal and resin (for example, see Patent Document 1), epoxy resin Attempts have also been made to improve the thermal conductivity of materials by adding a large amount of thermally conductive filler (see, for example, Patent Document 2).

JP 2000-091786 A JP 2004-10668 A

  However, in the method described in Patent Document 1, a metal sheet excellent in flexibility and flexibility is proposed by preparing a nonwoven fabric with metal fibers in advance and filling the voids with a thermoplastic resin containing a thermally conductive filler. However, since the material is produced using a metal non-woven fabric as a pillar, the ratio of the metal increases, which causes an increase in the weight of the product. Moreover, since it is necessary to produce the shape of a metal nonwoven fabric, the subject remained in the point that adjustment of the ratio of a metal fiber and resin was difficult.

  Moreover, in the method of patent document 2, the thermal conductivity is made to express 1.2 W / mK or more by the compounding quantity of a heat conductive filler adding 80 weight% or more in an epoxy resin. However, since it is relatively expensive and the filling ratio of the heat conductive filler having a large specific gravity of 2 or more is high, depending on the amount of filler added, it may cause an increase in product weight, cost, strength and moldability. The problem was left in the point of becoming.

  Under such circumstances, it is expected to create a material that has heat dissipating properties and can arbitrarily adjust such characteristics while having moldability superior to that of metal.

  An object of the present invention is to provide a composite resin composition that is superior in molding processability, lightness, and heat radiation to a metal material, and that is superior in thermal conductivity and mechanical strength in a planar direction to a resin material.

The above object is achieved by the following items (1) to (19).
(1) A composite resin composition containing (A) heat conductive fibers and (B) resin as constituent materials, and a plane measured by a laser flash method in a molded product obtained by molding the resin composition The thermal conductivity in the direction is 5 W / mK or more, the thermal conductivity in the thickness direction is less than half of the thermal conductivity in the plane direction, and the bending strength measured in accordance with JIS K 6911 is 80 MPa or more. The elastic modulus is 8 GPa or more, the specific gravity measured in accordance with JIS K 6911 is 1 to 5, and the linear expansion coefficient in the plane direction is 0.1 ppm / ° C. to 50 ppm / ° C. Composite resin composition.

(2) The composite resin composition according to item (1), wherein the thermal conductivity of the thermal conductive fiber (A) is 10 W / mK or more.

(3) The composite resin composition as described in (1) or (2), wherein the (A) heat conductive fiber has an average fiber length of 500 μm or more and 10 mm or less.

(4) Content of said (A) heat conductive fiber is 10 to 90 mass% of the whole composite resin composition, Any of (1) to (3) A composite resin composition according to claim 1.

(5) The composite resin composition according to any one of (1) to (4), wherein the (A) thermally conductive fiber includes a metal fiber.

(6) The composite resin composition as described in (5), wherein the metal element constituting the metal fiber contains at least one metal element selected from aluminum, copper, silver and iron.

(7) (C) The composite resin composition according to any one of items (1) to (6), further comprising fibers other than (A) the heat conductive fiber.

(8) The fibers of the component (C) other than the (A) heat conductive fibers are regenerated fibers such as rayon fibers, semi-synthetic fibers such as cellulose fibers, wood fibers made of conifers and hardwoods, cotton, hemp, Synthetic fibers such as natural fibers such as wool, polyamide fibers, aramid fibers, polyimide fibers, polyvinyl alcohol fibers, polyester fibers, acrylic fibers, polyparaphenylene benzoxazole fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, ethylene vinyl alcohol fibers And at least one fiber selected from inorganic fibers such as glass fiber and ceramic fiber.

(9) The composite resin composition according to any one of items (1) to (8), wherein the average particle size of the resin (B) is 500 μm or less.

(10) A composite resin obtained by dispersing a constituent material in a solvent, adding a polymer flocculant, aggregating the constituent material in a floc form, separating the aggregate from the solvent, and then removing the solvent. The composite according to any one of (1) to (9), wherein the composition further comprises (D) a powdery substance having ion exchange capacity as the constituent material. Resin composition.

(11) The powdery substance having ion exchange capacity (D) is at least one intercalation compound selected from clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica. The composite resin composition according to item (10), which is characterized.

(12) The powdery substance having ion exchange capacity (D) contains at least one clay mineral selected from smectite, halloysite, kanemite, kenyanite, zirconium phosphate and titanium phosphate (10) A composite resin composition as described in 1. above.

(13) The (D) powdery substance having ion exchange capacity contains at least one smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, soconite and stevensite. (10) The composite resin composition according to item.

(14) The composite resin composition according to item (10), wherein the powdery substance having ion exchange capacity (D) contains montmorillonite.

(15) Item (10) to Item (D), wherein the content of the powdery substance having ion exchange capacity (D) is 0.1% by mass or more and 30% by mass or less of the entire composite resin composition. (14) The composite resin composition according to any one of items.

(16) The composite resin composition according to any one of (1) to (15), further comprising (E) at least one filler powder selected from inorganic powders and metal powders. object.

(17) The metal element constituting the metal powder includes at least one metal element selected from aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum, and tungsten. The composite resin composition according to item (16).

(18) The composite resin composition according to any one of (10) to (17), wherein the solvent has a boiling point of 50 ° C. or higher and 200 ° C. or lower.

(19) A molded article excellent in thermal conductivity, comprising the composite resin composition according to any one of items (1) to (18).

  According to the present invention, it is possible to obtain a composite resin composition that is superior in molding processability, lightness, and heat radiation properties to metal materials, and that is superior in heat dissipation properties and mechanical strength in the planar direction to resin materials. Moreover, according to this invention, the composite resin composition excellent in the heat dissipation in a plane direction with respect to the thickness direction can be obtained.

The composite resin composition of the present invention is a composite resin composition containing (A) thermally conductive fibers and (B) resins as constituent materials, and a laser flash in a molded product obtained by molding the resin composition Bending strength measured in accordance with JIS K 6911, the thermal conductivity in the plane direction measured by the method is 5 W / mK or more, the thermal conductivity in the thickness direction is less than half the thermal conductivity in the plane direction Is 80 MPa or more, the flexural modulus is 8 GPa or more, the specific gravity measured in accordance with JIS K 6911 is 1 to 5, and the linear expansion coefficient in the plane direction is 0.1 pp.
m / ° C. or more and 50 ppm / ° C. or less. By adopting such a configuration, it is possible to obtain a composite resin composition that is superior in molding processability, lightness, and heat radiation than metal materials, and that is superior in heat dissipation in the planar direction and mechanical strength than resin materials. it can. Hereinafter, the present invention will be described in detail.

  The composite resin composition of the present invention preferably has a thermal conductivity in the plane direction measured by a laser flash method of 5 W / mK or more, preferably 10 W / mK or more, in a molded product obtained by molding the composite resin composition. Are more preferable, and those of 20 W / mK or more are particularly preferable. By setting it to the above lower limit value or more, a molded article having excellent thermal conductivity can be obtained. The composite resin composition of the present invention preferably has a thickness-wise thermal conductivity of a molded product obtained by molding the composite resin composition that is half or less than the thermal conductivity in the plane direction. Thereby, since heat can be selectively dissipated in the plane direction, it can be usefully used for a housing or the like. In the present invention, the shape of the test piece for measuring the thermal conductivity by the laser flash method is not particularly limited. For example, a 1.5 mm thick molded body can be used.

  In the present invention, the plane direction means that (A) thermally conductive fibers are distributed in the xy-axis direction of the molded body, and the thickness direction means the z-axis direction of the molded body, and (A) thermal conductivity. It shows that the direction is perpendicular to the distribution of the fiber in the molded body. A method for obtaining a test piece for thermal conductivity evaluation using a composite resin composition is not particularly limited. For example, press molding, compression molding, calendar roll molding, SMC method, injection molding, matched die method Further, a molded product formed by a molding method such as lamination molding with metal, resin, woven fabric, nonwoven fabric, or the like may be used as it is, or a test piece may be cut out from the obtained molded product and used. At this time, when a molded product is made of a thermosetting resin as the constituent material (B) resin, an annealing treatment is performed for about 1 to 6 hours within a range of about ± 20 ° C. with respect to the molding temperature. It is preferable.

  The composite resin composition of the present invention preferably has a bending strength measured in accordance with JIS K 6911 of 80 MPa or more, more preferably 120 MPa or more, in a molded product obtained by molding the composite resin composition. The above is particularly preferable. By setting it to the above lower limit or more, a molded article having excellent strength can be obtained. Moreover, the composite resin composition of the present invention preferably has a flexural modulus of 8 GPa or more measured in accordance with JIS K 6911, more preferably 10 GPa or more, in a molded product obtained by molding the composite resin composition. Preferably, it is 12 GPa or more. By setting it to the above lower limit or more, a molded article having excellent rigidity can be obtained.

  The composite resin composition of the present invention preferably has a specific gravity of 1 or more and 5 or less, more preferably 1 or more and 4 or less, in a molded product obtained by molding the composite resin composition. Those having 1 or more and 2 or less are particularly preferable. By setting it to the upper limit value or less, a molded article having excellent lightness can be obtained. In addition, when a texture is required, a material having a large specific gravity may be required. In such a case, a material having a specific gravity of 3 to 5 is preferable.

  The composite resin composition of the present invention preferably has a linear expansion coefficient in the plane direction of from 0.1 ppm / ° C. to 50 ppm / ° C., preferably from 1 ppm / ° C. to 45 ppm / ° C., in a molded product obtained by molding the composite resin composition. What is below is more preferable and what is 3 ppm / degrees C or more and 40 ppm / degrees C or less is especially preferable. By setting it to the upper limit value or less, a molded body excellent in low stress can be obtained.

In order to make the thermal conductivity, bending strength, flexural modulus, specific gravity and linear expansion coefficient in the molded product obtained by molding the composite resin composition of the present invention within the above-mentioned ranges, the composite resin composition (A) The type and shape of the thermally conductive fiber, the type and shape of the resin, and the blending ratio of the (A) thermally conductive fiber and the (B) resin. It can be adjusted by, for example.

  Among these, from the viewpoint of improving the thermal conductivity in the planar direction in the molded product obtained by molding the composite resin composition, (A) the thermal conductivity of the thermal conductive fiber is 10 W / mK or more. It is preferable to use it. In the present invention, (A) the method of measuring the thermal conductivity of the heat conductive fiber can measure, for example, a plate test piece material of the same material as the heat conductive fiber by a laser flash method.

  (A) The average fiber length of the thermally conductive fibers is not particularly limited, and is preferably selected as appropriate according to the required characteristics. For example, it is preferably 500 μm or more and 10 mm or less. From the viewpoint of molding processability, it is more preferably 500 μm or more and 3 mm or less, and from the viewpoint of improving thermal conductivity in the planar direction, it is particularly preferably 3 mm or more and 8 mm or less. When the average fiber length is less than the above lower limit, the fiber length is too short, and it becomes difficult for the heat conductive fibers to form a network, and thus the thermal conductivity in the planar direction may be difficult to express. Further, if the average fiber length exceeds the above upper limit, it is effective for the thermal conductivity in the planar direction, but it is not preferable because it causes a decrease in moldability. In addition, when using several heat conductive fiber from which average fiber length differs, it is possible to use that whose average fiber length is less than the said lower limit as a part. In this case, the moldability can be improved without impairing the metal properties due to the use of long fibers.

  (A) The content of the thermally conductive fiber is not particularly limited, and is preferably set as appropriate according to the required requirements. However, when the processability, lightness, and heat radiation of the resin are required. The composite resin composition is preferably 10% by mass or more and less than 30% by mass of the total content, and when it is required that the heat dissipation effect and the moldability are expressed in a balanced manner, the composite resin composition It is preferable that the total content is 30% by mass or more and less than 60% by mass. When a high heat dissipation effect is required, the total content of the composite resin composition is 60% by mass or more and less than 90% by mass. It is desirable. When the content of the composite resin composition is less than 10% by mass, lightness, workability, and thermal radiation are improved, but it is difficult for the thermal conductivity in the planar direction of the molded body to be 5 W / mK or more. . On the other hand, when the content is more than 90% by mass of the total content of the composite resin composition, the thermal conductivity in the planar direction is improved, but it is not preferable because the lightness, workability, and thermal radiation are deteriorated.

  (A) Although it will not specifically limit if it is a fiber which has heat dissipation as a heat conductive fiber, For example, a metal fiber, carbon fiber, etc. are mentioned. Among these, metal fibers and pitch-based carbon fibers are preferable from the viewpoint of the heat dissipation effect.

  The metal fiber may be a metal fiber composed of a single metal element or an alloy fiber composed of a plurality of metals, but examples of the metal element constituting the metal fiber include aluminum, Silver, copper, iron, etc. are mentioned.

  (A) As a heat conductive fiber, for example, Nippon Seisen Co., Ltd. and Bekaert Japan Co., Ltd. stainless fiber, Nigi Co., Ltd. copper fiber, aluminum fiber, brass fiber, steel fiber, titanium fiber, Phosphor bronze fibers and the like are available as commercial products, but are not limited thereto. These metal fibers may be used individually by 1 type, or may use 2 or more types together. Of these, copper fiber, aluminum fiber, and brass fiber are particularly preferable.

(A) The heat conductive fiber may be used as it is, but it may be surface-treated with a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, etc. depending on the required properties, You may use what performed the sizing agent process in order to improve a handleability.

  Depending on the required properties required, (C) fibers other than (A) thermally conductive fibers can be further included. (A) The fibers other than the fibers (C) are not particularly limited. For example, natural fibers such as wood fibers, cotton, hemp and wool, regenerated fibers such as rayon fibers, and semi-synthetic materials such as cellulose fibers. Fiber, polyamide fiber, aramid fiber, polyimide fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, polyparaphenylene benzoxazole fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, synthetic fiber such as ethylene vinyl alcohol fiber, and glass Examples thereof include inorganic fibers such as fibers and ceramic fibers. These fibers may be used alone or in combination of two or more. Of these, polyamide fibers, aramid fibers, polyimide fibers, polyparaphenylene benzoxazole fibers and the like are preferable from the viewpoint of improving bending strength, and inorganic fibers such as glass fibers and ceramic fibers are preferable from the viewpoint of improving bending elastic modulus. preferable.

  Examples of (C) fibers other than (A) fibers include, for example, Kevlar (registered trademark), which is an aramid fiber manufactured by Toray DuPont Co., Ltd., and Technora (registered trademark), which is an aramid fiber of Teijin Techno Products Co., Ltd. , Vinylon, a polyvinyl alcohol fiber manufactured by Kuraray Co., Ltd., Zylon (registered trademark), a polyparaphenylene benzoxazole fiber manufactured by Toyobo Co., Ltd., a glass fiber manufactured by Nittobo Co., Ltd. Dencaarcene, which is an alumina fiber, is available as a commercial product, but is not limited thereto.

  (A) The shape of the fiber other than the fiber (C) can be used without any particular limitation, and a shape according to the required characteristics can be used, but the strength characteristics such as bending strength and impact resistance can be used. For improvement, it is desirable to use chopped strands. In addition, in order to obtain the yield improvement effect, fibers that are beaten by mechanical shearing force such as a beater or homogenizer, or those that are fibrillated increase the fiber surface area and physically capture the constituent materials. It is desirable to use it because the effect of improving the ability and the effect that the polymer flocculant easily acts chemically are obtained.

  The (B) resin that is a constituent material of the composite resin composition of the present invention may be a thermoplastic resin or a thermosetting resin, and is particularly limited as long as it can act as a binder. For example, acrylonitrile-styrene copolymer (AS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate, polystyrene, polyvinyl chloride, polyester resin, polyamide, polyphenylene sulfide (PPS). ) Thermosetting resins such as resins, acrylic resins, polyethylene, polypropylene, fluororesins, and the like, phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, and polyurethanes. These resins can be appropriately selected and used according to the required properties, and may be used alone or in combination of two or more. Among these, in terms of good mechanical strength and chemical resistance, thermosetting resins are preferable, in terms of good moldability and design properties such as resin transparency, Thermoplastic resins are preferred.

(B) As a preferable form for using the resin, a solid state having an average particle diameter of 500 μm or less or an emulsion is desirable. More preferably, the average particle size is about 1 nm to 300 μm. Thereby, when the polymer flocculant is added, (B) the resin and (A) the heat conductive fiber are likely to form an agglomerated state in the presence of a powdery substance having ion exchange capacity (D) described later. , The yield is improved. When the average particle size is larger than the above upper limit value, it becomes difficult to form an aggregated state even if a polymer flocculant is added, which causes a decrease in yield. The average particle diameter of the resin (B) is determined, for example, by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as the average particle diameter based on a 50% particle diameter. be able to.

  The method for producing the composite resin composition of the present invention is not particularly limited, but after the constituent materials are dispersed in a solvent, a polymer flocculant is added to cause the constituent materials to aggregate in a floc form. A method of removing the solvent after separating the product from the solvent is preferred. The method for dispersing the constituent materials and the like in the solvent is not particularly limited, and examples thereof include a method of stirring with a disperser or a homogenizer. In addition, the method for separating and removing the aggregate from the solvent is not particularly limited, but for example, after separating only by passing the solvent using a net or woven fabric such as metal or plastic, non-woven fabric, Further, there may be mentioned a method of removing the agglomerates by removing the solvent and drying using a press or a dryer. In such a method for producing a composite resin composition, it is more preferable that (D) a powdery substance having ion exchange capacity is further included as a constituent material. In such a method for producing a composite resin composition, (D) by using a powder substance having ion exchange capacity, (A) a high yield while keeping the fiber length of the heat conductive fiber long, (A) heat Since the aggregate of conductive fiber and (B) resin can be produced efficiently, the blending ratio of (A) thermally conductive fiber and (B) resin can be adjusted over a wide range. For this reason, according to the required request, (A) excellent balance between characteristics such as thermal conductivity and rigidity of the thermal conductive fiber and (B) characteristics such as processability, lightness and thermal radiation of the resin A wide range of composite resin compositions can be obtained more efficiently.

  (D) The powdery substance having ion exchange ability is preferably at least one intercalation compound selected from clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica.

  The clay mineral is not particularly limited as long as it has ion exchange ability, and examples thereof include smectite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. The hydrotalcite is not particularly limited as long as it has ion exchange capacity, and examples thereof include hydrotalcite and hydrotalcite-like substances. The fluorine teniolite is not particularly limited as long as it has ion exchange ability, and examples thereof include lithium-type fluorine teniolite and sodium-type fluorine teniolite. The swellable synthetic mica is not particularly limited as long as it has ion exchange ability, and examples thereof include sodium tetrasilicon fluorine mica and lithium tetrasilicon fluorine mica. These intercalation compounds may be natural products or those synthesized, and may be used alone or in combination of two or more. Among these, clay minerals are more preferable, and smectite is more preferable in that it exists from natural products to synthetic products and has a wide range of selection.

  The smectite is not particularly limited as long as it has ion exchange ability, and examples thereof include montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, and stevensite. Montmorillonite is a hydrated silicate of aluminum, but may be bentonite containing montmorillonite as a main component and minerals such as quartz, mica, feldspar, and zeolite. Synthetic smectite with few impurities is preferable when used for applications such as coloring and impurities.

  (D) As a powdery substance having ion exchange capacity, for example, Kunipia (bentonite) manufactured by Kunimine Industry Co., Ltd., Smecton SA (synthetic saponite), Sun Lovely (scale-like silica fine particles) manufactured by AGC S-Itech Co., Ltd. , Somasif (swelling synthetic mica), Lucentite (synthetic smectite) manufactured by Corp Chemical Co., Ltd. However, it is not limited to these.

  (D) The content of the powdery substance having ion exchange capacity is preferably 0.1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less of the entire composite resin composition. It is. If it is in the said range, the effect which improves the fixability of the structural material from which a property differs like (A) heat conductive fiber and (B) resin can be acquired. According to the ratio of (A) thermally conductive fiber and (B) resin in the constituent material, and the type and amount of the polymer flocculant, (D) the content of the powdery substance having ion exchange capacity Is preferably adjusted.

  The solvent used for dispersing the constituent materials in the present invention is not particularly limited, but it is difficult to volatilize during the process, it is easy to remove the solvent because it does not remain in the product, and if the boiling point is too high, the solvent is removed. Therefore, from the standpoint of enormous energy consumption, those having a boiling point of 50 ° C. or more and 200 ° C. or less are preferable. Examples of such a material include water, ethanol, 1-propanol, 1-butanol, Alcohols such as ethylene glycol, ketones such as acetone, methyl ethyl ketone, 2-heptanone, cyclohexanone, esters such as ethyl acetate, butyl acetate, methyl acetoacetate, methyl acetoacetate, tetrahydrofuran, isopropyl ether, dioxane, furfural And ethers. These solvents may be used alone or in combination of two or more. Among these, water is particularly preferable because of its abundant supply amount, low cost, low environmental load, high safety and easy handling.

  The polymer flocculant used for aggregating the constituent materials of the composite resin composition of the present invention in a floc form is not particularly limited by ionicity and the like. Cationic polymer flocculant, anionic polymer A flocculant, a nonionic polymer flocculant, an amphoteric polymer flocculant, and the like can be used. Examples of such a material include cationic polyacrylamide, anionic polyacrylamide, Hoffman polyacrylamide, mannic polyacrylamide, amphoteric copolymerized polyacrylamide, cationized starch, amphoteric starch, and polyethylene oxide. These polymer flocculants may be used alone or in combination of two or more. Further, as the polymer flocculant, the polymer structure, molecular weight, functional group amount such as hydroxyl group and ionic group, etc. can be used without particular limitation depending on the required properties.

  Examples of the polymer flocculant include polyethylene oxide manufactured by Wako Pure Chemical Industries, Ltd., Kanto Chemical Co., Ltd., Sumitomo Seika Co., Ltd., and cationic PAM manufactured by Harima Kasei Co., Ltd. Fix, Hermide B-15 which is an anionic PAM, Hermide RB-300 which is an amphoteric PAM, SC-5 which is a cationized starch manufactured by Sanwa Starch Co., Ltd. are commercially available. It is not limited.

  The amount of the polymer flocculant added is not particularly limited, but is preferably 100 ppm by mass or more and 1% by mass or less based on the weight of the constituent material. More preferably, it is 500 mass ppm or more and 0.5 mass%. Thereby, the constituent material can be aggregated with good yield. If the addition amount of the polymer flocculant is smaller than the above lower limit value, the yield may be lowered, and if it is larger than the above upper limit value, the agglomeration is too strong and problems such as dehydration may occur.

The composite resin composition of the present invention can be adjusted in characteristics by further including (E) at least one filler powder selected from inorganic powders and metal powders as a constituent material. Examples of the inorganic powder include oxides such as titanium oxide, alumina, silica, zirconia, and magnesium oxide, nitrides such as boron nitride, aluminum nitride, and silicon nitride, and barium sulfate, iron sulfate, and copper sulfate. Examples include sulfides, hydroxides such as aluminum hydroxide and magnesium hydroxide, minerals such as kaolinite, talc, natural mica, and synthetic mica, and carbides such as silicon carbide. However, a surface treated with a silane coupling agent, an aluminate coupling agent, a titanate coupling agent or the like may be used depending on the required characteristics.

  Further, the metal powder may be a metal powder composed of a single metal element or an alloy powder composed of a plurality of metals, but the metal element constituting the metal powder may be aluminum, Examples thereof include silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum, and tungsten.

  The composite resin composition of the present invention includes the above-mentioned (A) heat conductive fiber, (B) resin, (C) fiber, (D) powdery substance having ion exchange capacity, (E) inorganic powder, and metal powder. In addition to at least one filler powder selected from the group consisting of polymer flocculants, stabilizers such as antioxidants and ultraviolet absorbers for the purpose of improving properties, mold release agents, plasticizers, flame retardants, and resin curing catalysts And curing accelerators, pigments, dry paper strength improvers, wet strength strength improvers, yield improvers, drainage improvers, size fixers, antifoaming agents, rosin sizing agents for acidic papermaking, Neutral paper rosin sizing agent, alkyl ketene dimer sizing agent, alkenyl succinic anhydride sizing agent, special modified rosin sizing agent, coagulant such as sulfate band, aluminum chloride, polyaluminum chloride, etc. The production condition adjustment , It may be used various additives for the purpose of expressing the required physical properties.

  As described above, the composite resin composition used in the present invention is obtained by dispersing constituent materials and the like in a solvent, and then adding a polymer flocculant to aggregate the constituent materials and the like in a floc form, and separating the aggregate from the solvent. After removing the solvent, it can be obtained by removing the solvent. However, the method is not limited to this method, and a composite resin composition is formed by impregnating a resin by forming a heat conductive fiber and a web with a card machine or the like. And a method of blending thermally conductive fibers in the resin.

  Next, the manufacturing method of the molded object of this invention is demonstrated. The method for producing the molded body of the present invention is not particularly limited, and for example, press molding, compression molding, calender roll molding, SMC method, injection molding, matched die method, metal, resin, woven fabric, nonwoven fabric, etc. And a molding method such as lamination molding.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Further, “parts” described in Examples and Comparative Examples indicate “parts by mass”, and “%” indicates “% by mass”.
The raw materials described in the examples are expressed in parts by mass excluding the moisture content contained in advance.

1. Preparation of composite resin composition (1) Example 1
24 parts of epoxy resin 1002 (Mitsubishi Chemical Co., Ltd.) pulverized with a high-pressure homogenizer to an average particle size of 30 μm, 1 part of imidazole epoxy resin curing agent 2PZ-PW (manufactured by Shikoku Kasei Co., Ltd.), synthetic saponite (Kunimine) Industrial Co., Ltd., trade name Smecton SA (5 parts), fiber length 3 mm, fiber diameter 60 μm aluminum fiber (manufactured by Niji Gi Co., Ltd., material: A1070), cellulose pulp (Nippon Paper Chemicals Co., Ltd., trade name NDPT) ) After adding 10 parts to 10,000 parts of water and stirring with a disperser for 30 minutes, cationized starch SC-5 manufactured by Sanwa Starch Co., Ltd. dissolved in water in advance was added to the constituent materials by 0.1%. A 4% weight addition is performed to agglomerate the constituent materials in floc form. The agglomerates are separated from water with a 40-mesh metal mesh, and then the agglomerates are depressurized and further dried in a dryer at 100 ° C. for 4 hours to obtain a composite resin composition with a yield of 94%. Got in. Details of the yield measurement method will be described later.

(2) Example 2
10 parts of epoxy resin 1002 (manufactured by Mitsubishi Chemical Co., Ltd.) pulverized with a high-pressure homogenizer to an average particle size of 30 μm, 1 part of imidazole-based epoxy resin curing agent 2PZ-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), synthetic saponite ( 3 parts by Kunimine Kogyo Co., Ltd., trade name Smecton SA, 82 parts copper fiber (manufactured by Nijigi Co., Ltd.) with a fiber length of 3 mm and a fiber diameter of 60 μm, 4 parts cellulose pulp (trade name NDPT made by Nippon Paper Chemicals Co., Ltd.) Is added to 10000 parts of water, stirred with a disperser for 30 minutes, and then added with 0.3% of cationized starch SC-5 manufactured by Sanwa Starch Co., Ltd. dissolved in water to the constituent materials. And the constituent materials are aggregated in a floc form. The agglomerates are separated from water with a 40 mesh metal net, and then the agglomerates are depressurized and further dried in a dryer at 100 ° C. for 4 hours to obtain a composite resin composition with a yield of 95%. I got it.

(3) Example 3
40 parts of a solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 5 parts bentonite (trade name Kunipia manufactured by Kunimine Industries Co., Ltd.) pulverized to an average particle size of 100 μm by an atomizer pulverizer, fiber length 3 mm, fiber diameter 25 parts of 90 μm aluminum fibers (manufactured by Nijigi Co., Ltd., material: A1070), 5 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products Co., Ltd.) )) 25 parts is added to 10,000 parts of water, stirred with a disperser for 30 minutes, and then a polyethylene oxide molecular weight of 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in water is constructed. Add 0.2% to the material to agglomerate the constituent materials in floc form. The agglomerates are separated from water with a 40-mesh metal mesh, and then the agglomerates are dehydrated and pressed and further dried in a 70 ° C. drier for 6 hours to obtain a composite resin composition with a yield of 97%. Got in.

(4) Example 4
35 parts of solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 5 parts bentonite (trade name Kunipia manufactured by Kunimine Industries Co., Ltd.) pulverized to an average particle size of 100 μm by an atomizer pulverizer, fiber length 3 mm, fiber diameter 40 parts of 90 μm aluminum fiber (manufactured by Niji Gi Co., Ltd., material: A1070), 5 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products Co., Ltd.) ) Made by adding 15 parts to 10000 parts of water, stirring with a disperser for 30 minutes, and preliminarily dissolved in polyethylene in a molecular weight of 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) Add 0.5% to the material to agglomerate the constituent materials in floc form. The agglomerates are separated from water with a 40-mesh metal mesh, and then the agglomerates are depressurized and placed in a drier at 70 ° C. for 6 hours to dry the composite resin composition with a yield of 94%. Got in.

(5) Example 5
35 parts of solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 5 parts bentonite (trade name Kunipia manufactured by Kunimine Industries Co., Ltd.) pulverized to an average particle size of 100 μm by an atomizer pulverizer, fiber length 3 mm, fiber diameter 40 parts of 90 μm aluminum fiber (manufactured by Nijiki Co., Ltd., material: A5052), 5 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products Co., Ltd.) ) Made by adding 15 parts to 10000 parts of water, stirring with a disperser for 30 minutes, and preliminarily dissolved in polyethylene in a molecular weight of 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) Add 0.5% to the material to agglomerate the constituent materials in floc form. The agglomerates are separated from water with a 40-mesh metal mesh, and then the agglomerates are depressurized and placed in a drier at 70 ° C. for 6 hours to dry the composite resin composition with a yield of 94%. Got in.

(6) Example 6
30 parts of pulverized acrylonitrile-styrene copolymer (AS) resin (trade name Sebian N, manufactured by Daicel Industries, Ltd.) pulverized with a freeze pulverizer to an average particle size of 200 μm, and flaky silica fine particles (AGC S-Tech ( Product name Sun Lovely Co., Ltd.) 5 parts, fiber length 3 mm, fiber diameter 90 μm copper fiber (manufactured by Nigi Co., Ltd.) 10 parts, average particle diameter 20 μm copper powder (trade name, manufactured by Kojundo Chemical Laboratory Co., Ltd.) CUE13PB) 40 parts, fiber diameter 22 μm, fiber length 5 mm polyvinyl alcohol fiber (trade name vinylon made by Kuraray Co., Ltd.) 15 parts was added to 10000 parts of water, stirred with a disperser for 30 minutes, Add dissolved cationic polyacrylamide (manufactured by Harima Kasei Co., Ltd.) to a weight of 0.5% with respect to the component material, and then block the component material. It is aggregated to. The agglomerates are separated from water with an 80-mesh metal mesh, and then the agglomerates are depressurized and further placed in a drier at 130 ° C. for 6 hours to dry the composite resin composition at a yield of 90%. Got in.

(7) Comparative Example 1
Using a lab plast mill, 40 parts of a solid resole resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 60 parts of aluminum powder having an average particle diameter of 100 μm (trade name ALE02PB manufactured by Kojundo Chemical Laboratory Co., Ltd.) It was melt-kneaded at 100 ° C. for 5 minutes at a rotation speed of 50 rpm, and a composite resin composition was obtained in a yield of 99%.

(8) Comparative Example 2
Using a lab plast mill, 25 parts of a solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 75 parts of aluminum powder having an average particle diameter of 100 μm (trade name ALE02PB manufactured by Kojundo Chemical Laboratory Co., Ltd.) It was melt-kneaded at 100 ° C. for 5 minutes at a rotation speed of 50 rpm, and a composite resin composition was obtained in a yield of 99%.

(9) Comparative Example 3
15 parts by mass of epoxy resin 1002 (manufactured by Mitsubishi Chemical Co., Ltd.), 1 part by mass of imidazole-based epoxy resin curing agent 2PZ-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), copper powder having an average particle diameter of 20 μm (Co., Ltd.) 84 parts of a trade name CUE13PB) manufactured by Pure Chemical Laboratories were melt kneaded at 100 ° C. for 5 minutes at a rotation speed of 50 rpm using a lab plast mill to obtain a composite resin composition at a yield of 99%.

2. Fabrication of molded body (1) Example 7
The composite resin composition obtained in Example 1 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 160 ° C. for 60 minutes under a surface pressure of 10 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(2) Example 8
The composite resin composition obtained in Example 2 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 160 ° C. for 60 minutes under a surface pressure of 10 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(3) Example 9
The composite resin composition obtained in Example 3 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 180 ° C. for 10 minutes under a surface pressure of 30 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(4) Example 10
The composite resin composition obtained in Example 4 was set in a mold coated with a release agent, and compression molding was performed on the composite resin composition at a surface pressure of 30 MPa at 180 ° C. for 10 minutes. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(5) Example 11
The composite resin composition obtained in Example 5 was set in a mold coated with a release agent, and compression molding was performed on the composite resin composition at a surface pressure of 30 MPa at 180 ° C. for 10 minutes. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(6) Example 12
The composite resin composition obtained in Example 6 was set in a mold coated with a release agent, and compression molding was performed on the composite resin composition at 200 ° C. for 10 minutes under a surface pressure of 10 MPa. The mold was cooled to 0 ° C. to obtain a molded body having a length of 10 cm × width of 10 cm × thickness of 2 mm.

(7) Comparative Example 4
The composite resin composition obtained in Comparative Example 1 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 180 ° C. for 10 minutes under a surface pressure of 5 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(8) Comparative Example 5
The composite resin composition obtained in Comparative Example 2 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 180 ° C. for 10 minutes under a surface pressure of 5 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(9) Comparative Example 6
The composite resin composition obtained in Comparative Example 3 was set in a mold coated with a release agent, and the composite resin composition was subjected to compression molding at 160 ° C. for 60 minutes under a surface pressure of 3 MPa. A molded body having a size of 10 cm × width 10 cm × thickness 2 mm was obtained.

(10) Comparative Example 7
What cut out the board of length 4cm x width 4cm x thickness 1mm from the aluminum plate (material: A1070) was used.

(11) Comparative Example 8
A polycarbonate plate (length 4 cm × width 4 cm × thickness 1 mm) manufactured by Takiron Co., Ltd. was used.

  The characteristic evaluation shown below was performed using the molded bodies obtained in Examples 7 to 12 and Comparative Examples 4 to 6. The results are shown in Table 1.

3. Evaluation method of characteristics (Part 1)
3.1 Composite resin composition (1) Yield Calculated according to the following formula.
Yield (%) = (weight of obtained composite resin composition / total weight of prepared composite resin composition material) × 100
About the obtained composite resin composition, the weight after drying was used, and the total weight of the prepared composite resin composition raw material was the amount from which moisture was removed.

3.2 Molded body (1) Specific gravity measurement The specific gravity measurement was performed in accordance with JIS K 6911 (General test method for thermosetting plastics). The test piece used was cut from the molded body so as to be 2 cm long × 2 cm wide × 2 mm thick.

(2) Measurement of thermal conductivity For measurement in the planar direction, the molding time was tripled with respect to the molding conditions for obtaining a molded product of 10 cm in length × 10 cm in width × 2 mm in thickness, 10 mm in length × 10 mm in width × length A 3 cm shaped body was obtained. Moreover, for the thickness direction measurement, a molded body having a length of 10 cm, a width of 10 cm, and a length of 1.5 mm was obtained under the same molding conditions as those for obtaining a molded body having a length of 10 cm, a width of 10 cm, and a thickness of 2 mm. Each obtained molded body was cut out to be 10 mm long × 10 mm wide × 1.5 mm long to obtain a test piece. Next, the thermal conductivity in the length direction of the plate-shaped test piece was measured by a laser flash method using a Xe flash analyzer LFA447 manufactured by NETZSCH. The measurement was performed at 25 ° C. in an air atmosphere.

(3) Bending test The bending test was performed in accordance with JIS K 6911 (thermosetting plastic general test method). The test piece used was cut from the molded body so as to be 50 mm long × 25 mm wide × 2 mm thick. The distance between fulcrums in the bending test was 32 mm.

(4) Measurement of coefficient of linear expansion A molded body of 5 mm length × 30 mm width × 10 mm length is produced by multiplying only the molding time by 3 times the molding conditions for obtaining a molded body of 10 cm long × 10 cm wide × 2 mm thick. Then, it was cut into a test piece of 5 mm length × 5 mm width × 10 mm length, and the linear expansion coefficient in the length direction was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA-6000). The rate of temperature increase was 5 ° C./min, and the linear expansion coefficient (α1) was determined in the temperature range of 80 to 120 ° C.

  Using the molded bodies obtained in Examples 9 and 10 and Comparative Examples 7 and 8, the following characteristic evaluation was performed. The results are shown in Table 2.

4). Evaluation method of characteristics (Part 2)
4.1 Molded body (1) Measurement of infrared emissivity After the test piece was heated to reach an equilibrium temperature, Examples 9 and 10 and Comparative Example 8 were used using an FT-IR (Fourier transform infrared spectroscopic hardness meter). Was measured at a measurement temperature of 80 ° C., Comparative Example 7 was measured at a measurement temperature of 250 ° C. and a measurement wavelength of 4.4 μm to 15.4 μm, and an infrared spectrum was measured to obtain an integral emissivity (%). In addition, the test piece used what was cut out from the molded object so that it might become 4 cm long x 4 cm wide x 1 mm in thickness.

Examples 1 to 6 are composite resin compositions obtained by the present invention, and Examples 7 to 12 are molded articles obtained by the present invention.
In all of Examples 1 to 6, composite resin compositions were obtained in high yield. In Examples 7-12, the thermal conductivity in the plane direction is 5 W / mK or more, the thermal conductivity in the thickness direction is less than half the thermal conductivity in the plane direction, the bending strength is 80 MPa or more, and the bending It was found that a molded article having an excellent property balance was obtained with an elastic modulus of 8 GPa or more, a specific gravity of 1 to 5 and a linear expansion coefficient in the plane direction of 0.1 ppm / ° C. to 50 ppm / ° C.

When comparing the molded body of Example 7 and Comparative Example 4, it is an examination showing the difference between the fiber made of aluminum A1070 and the powder filler, and the volume ratio in the molded body as aluminum is almost the same. However, the molded product in which the heat conductive fibers according to the present invention were mixed with good distribution showed a result that the heat dissipation in the planar direction was 25 times or more higher than that of the powder filler filled high.
Moreover, in Examples 9-11, even if it uses organic fiber together, the heat conductivity to a plane direction is 5 W / mK or more, and even if it uses organic fiber together, heat conductivity is not impaired and favorable heat | fever. A molded article that exhibits conductivity and has good mechanical properties such as a bending strength of 200 MPa or more is obtained.

  Moreover, in the measurement result of infrared emissivity, it has confirmed that Example 9, 10 was a value excellent in comparison with the comparative example 7 which is an aluminum molded object.

  From the above results, it can be seen that the present invention makes it possible to obtain a molded article having an excellent balance between characteristics such as processability, lightness and thermal radiation and characteristics such as thermal conductivity and rigidity.

According to the present invention, it is possible to obtain a molded article having excellent balance of properties such as workability, lightness, thermal radiation, thermal conductivity, rigidity, and the like, and the thermal conductivity in the plane direction is more than double the thickness direction. Can do.
Therefore, the molded product obtained from the composite resin composition of the present invention is a personal computer, a mobile phone, a portable information terminal, a plasma display television, a liquid crystal television, an OA device, a game device, an entertainment product, an air conditioner, an audio, an optical device, and an illumination. Can be used for electronic products such as appliances, internal mechanical parts of automotive electronic products, components such as housings, and structural parts for construction, parts for aerospace, space, automobiles, etc. Thus, it is possible to contribute to improvement of fuel consumption and energy saving by weight reduction, elimination of heat spots such as electronic devices, and the like, and it is possible to reduce the environmental load.

Claims (19)

As a constituent material, a composite resin composition containing (A) a thermally conductive fiber and (B) a resin,
In the molded product obtained by molding the resin composition, the thermal conductivity in the planar direction measured by the laser flash method is 5 W / mK or more, and the thermal conductivity in the thickness direction is relative to the thermal conductivity in the planar direction. The bending strength measured in accordance with JIS K 6911 is 80 MPa or more, the flexural modulus is 8 GPa or more, the specific gravity measured in accordance with JIS K 6911 is 1 to 5, and JIS K 7197 A composite resin composition characterized by having a linear expansion coefficient in a plane direction measured in accordance with the above is from 0.1 ppm / ° C. to 50 ppm / ° C.   The composite resin composition according to claim 1, wherein the thermal conductivity of the (A) thermally conductive fiber is 10 W / mK or more.   The composite resin composition according to claim 1 or 2, wherein the (A) heat conductive fiber has an average fiber length of 500 µm or more and 10 mm or less.   4. The composite resin composition according to claim 1, wherein the content of the (A) heat conductive fiber is 10% by mass or more and 90% by mass or less of the entire composite resin composition. object.   The composite resin composition according to claim 1, wherein the (A) heat conductive fiber includes a metal fiber.   The composite resin composition according to claim 5, wherein the metal element constituting the metal fiber includes at least one metal element selected from aluminum, copper, silver, and iron.   (C) The composite resin composition according to any one of claims 1 to 6, further comprising a fiber other than the heat conductive fiber (A).   The fiber of the component (C) other than the (A) heat conductive fiber is a natural fiber such as wood fiber, cotton, hemp, wool, regenerated fiber such as rayon fiber, semi-synthetic fiber such as cellulose fiber, polyamide fiber, Synthetic fibers such as aramid fiber, polyimide fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber polyparaphenylene benzoxazole fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, ethylene vinyl alcohol fiber, glass fiber, ceramic fiber, etc. The composite resin composition according to claim 7, comprising at least one fiber selected from inorganic fibers.   The composite resin composition according to any one of claims 1 to 8, wherein the (B) resin has an average particle size of 500 µm or less.   A composite resin composition obtained by dispersing a constituent material in a solvent, adding a polymer flocculant, aggregating the constituent material in a floc form, separating the aggregate from the solvent, and then removing the solvent. The composite resin composition according to any one of claims 1 to 9, further comprising (D) a powdery substance having ion exchange ability as the constituent material.   (D) The powdery substance having ion exchange capacity is at least one intercalation compound selected from clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica. The composite resin composition according to 10. 11. The composite according to claim 10, wherein the powdery substance having ion exchange capacity (D) contains at least one clay mineral selected from smectite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Resin composition.   The powdery substance having ion exchange capacity (D) contains at least one smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, soconite and stevensite. The composite resin composition as described.   11. The composite resin composition according to claim 10, wherein the powdery substance having (D) ion exchange capacity contains montmorillonite.   The content of the powdery substance having the ion exchange capacity (D) is 0.1% by mass or more and 30% by mass or less of the entire composite resin composition. A composite resin composition as described in 1. above.   The composite resin composition according to any one of claims 1 to 15, further comprising (E) at least one filler powder selected from inorganic powders and metal powders as the constituent material.   The metal element constituting the metal powder includes at least one metal element selected from aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum, and tungsten. 16. The composite resin composition according to 16.   18. The composite resin composition according to claim 10, wherein the solvent has a boiling point of 50 ° C. or higher and 200 ° C. or lower. A molded article excellent in thermal conductivity, comprising the composite resin composition according to any one of claims 1 to 18.