JP5821267B2 - Method for producing composite material composition, composite material composition and molded body - Google Patents

Description

  The present invention relates to a method for producing a composite material composition, a composite material composition, and a molded body.

  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.

  Resins are mass-produced industrially because of their low specific gravity, excellent insulation, elasticity, dimensional stability, vibration absorption, corrosion and chemical resistance, and good workability. However, compared to metals, the strength and heat resistance are weak, the thermal conductivity and electrical conductivity are low, and they are easily charged with static electricity.

In order to compensate for the shortcomings of metals and resins, composite materials such as resin and glass fiber, such as FRP, have been developed. Since the specific gravity is relatively small and the strength and workability are good, It is popular.
In addition, studies have been made to suppress the shortcomings by taking advantage of the characteristics of each of the metal and the resin by filling the voids in the metal fiber non-woven fabric (see, for example, Patent Document 1).
In addition, since the specific gravity difference between resin and metal is too large, kneading with a single-screw or twin-screw extruder or kneader cannot be uniformly dispersed and segregates in the composite material, Metal fibers are cut by mechanical shearing force, and there are problems such as inability to express original characteristics. Metal and resin composite materials are produced by injection molding using a flexible thermoplastic resin as a matrix resin for metal fibers. The examination etc. which try to do is also tried (for example, refer patent document 2).

JP 2000-091786 A JP 2006-278574 A

  However, in the method described in Patent Document 1, an attempt is made to impregnate the resin in the voids of the metal nonwoven fabric. However, since the metal nonwoven fabric serves as a support of the molded body, the ratio of the metal nonwoven fabric as a whole of the composite material increases, and the weight It is difficult to cause an increase and to easily change the compounding ratio of the metal and the resin. In addition, since the shape of the nonwoven fabric is pre-formed, the flowability of the resin is limited when using it to produce a molding material, and the moldability is lower than that of short fiber-resin composite materials. Deteriorate.

  Further, in the method described in Patent Document 2, since a metal fiber is not cut by a mechanical shearing force, it is essential to use a flexible thermoplastic resin, the heat resistance of the molding material itself is lowered, or an appropriate amount of metal is reduced. Although a material with a small thickness can be formed by blending, there are problems such as an increase in the blending amount of the metal fibers that the molding process deteriorates.

Under such circumstances, there is a demand for an adjustable composite material without the resin and metal fibers being unevenly distributed in the composite material and without limiting the amount of each compound to the production method. The creation of materials that can manifest their properties is expected.

  Under these circumstances, investigations have been made to obtain a composite material composition by a method in which a constituent material containing metal fibers and a resin is dispersed in a solvent, and then aggregated in a floc form, and further the solvent is removed. It was difficult to fix metal fibers having a high specific gravity only by adding a flocculant. The present invention has found that the use of a powdery substance having ion exchange ability can greatly improve the fixability of constituent materials having different properties, such as metal fibers and resins, and based on this knowledge. It has been achieved through research. The objective of this invention is providing the manufacturing method of the metal fiber-resin composite material composition which can express the characteristic of a metal fiber and resin with sufficient yield, maintaining the fiber length of a metal fiber.

The above object is achieved by the following items (1) to (15).
(1) A composite material 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. A method for producing a composition, wherein the constituent material comprises (A) a powdery substance having ion exchange capacity, (B) a metal fiber, and (C) a resin. Method.

(2) The powdery substance having ion exchange capacity (A) is at least one intercalation compound selected from viscosity minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica. A method for producing a composite material composition according to item (1), which is characterized in that

(3) The powdery substance having ion exchange capacity (A) contains at least one clay mineral selected from smectite, halloysite, kanemite, kenyanite, zirconium phosphate and titanium phosphate (1) A method for producing the composite material composition according to item.

(4) The (A) powdery substance having ion exchange capacity contains at least one smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, soconite and stevensite. The manufacturing method of the composite material composition as described in (1) term.

(5) The method for producing a composite material composition according to item (1), wherein the powdery substance (A) having ion exchange capacity contains montmorillonite.

(6) Item (A) to Item (1), wherein the content of the powdery substance having ion exchange capacity (A) is 0.1% by mass or more and 30% by mass or less of the entire composite material composition. The manufacturing method of the composite material composition as described in any one of (5) term.

(7) The metal element constituting the metal fiber (B) includes at least one metal element selected from aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum, and tungsten. The method for producing a composite material composition according to any one of items (1) to (6), wherein:

(8) The content of the (B) metal fiber is 1% by mass or more and 90% by mass or less of the entire composite material composition, and any one of items (1) to (7) A method for producing the composite material composition according to item.

(9) The composite material composition according to any one of (1) to (8), wherein the average fiber length of the (B) metal fiber is 500 μm or more and 10 mm or less. Production method.

(10) The method for producing a composite material composition according to any one of (1) to (9), further comprising (D) a fiber other than (B) the metal fiber.

(11) The fiber of the component (D) other than the metal fiber (B) is a natural fiber such as wood fiber, cotton, hemp or wool, regenerated fiber such as rayon fiber, semi-synthetic fiber such as cellulose fiber, polyamide fiber , Synthetic fiber 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, carbon fiber, glass fiber, The method for producing a composite material composition according to item (10), comprising at least one fiber selected from inorganic fibers such as ceramic fibers.

(12) The method for producing a composite material composition according to any one of items (1) to (11), wherein the resin (C) has an average particle size of 500 μm or less.

(13) The method for producing a composite material composition according to any one of (1) to (12), wherein the solvent has a boiling point of 50 ° C. or higher and 200 ° C. or lower.

(14) A composite material composition obtained by the method for producing a composite material composition according to any one of items (1) to (13).

(15) A molded article using the composite material composition according to item (14).

  According to the present invention, the presence of a powder substance having an ion exchange ability can efficiently produce an aggregate of metal fibers and organic matter, with a high yield, while maintaining a long fiber length of the metal fibers, etc. A metal fiber-resin composite material composition having excellent isotropy can be obtained. Further, according to the present invention, the compounding amount of the metal fiber and the resin can be adjusted in a wider range than before, and the properties such as the processability and light weight of the resin and the heat conduction of the metal can be adjusted according to the required requirements. Can be obtained a wide range of composite materials having a good balance with properties such as properties, electromagnetic shielding properties, and rigidity.

  In the method for producing the composite material composition of the present invention, the constituent materials are dispersed in a solvent, a polymer flocculant is added, the constituent materials are aggregated in a floc form, and the aggregate is separated from the solvent. A method for producing a composite material composition obtained by removing the solvent, wherein the constituent material includes (A) a powdery substance having ion exchange capacity, (B) a metal fiber, and (C) a resin. Features. Moreover, the molded object of this invention is characterized by using the composite material composition obtained by said manufacturing method. By adopting these configurations, it is possible to adjust the blending amount of the metal fiber and the resin in a wider range than before, and according to the required requirements, characteristics such as resin processability and light weight, and the heat of the metal A wide range of composite material compositions and molded articles excellent in balance with properties such as conductivity, electromagnetic shielding properties and rigidity can be obtained. Hereinafter, the present invention will be described in detail.

  First, the composite material composition of the present invention will be described. The composite material composition of the present invention can contain (A) a powdery substance having ion exchange capacity, (B) a metal fiber, and (C) a resin as a constituent material. The powdery substance having ion exchange ability (A) that is a constituent material of the composite material composition of the present invention is at least selected from clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite, and swellable synthetic mica. A single intercalation compound is preferred.

  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.

  (A) As a powdery substance having ion exchange capacity, for example, Kunipia (bentonite) manufactured by Kunimine Industry Co., Ltd., Smecton SA (synthetic saponite), Sunlabry (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.

  (A) 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 material 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 (B) metal fiber and (C) resin can be acquired. In addition, the content of (A) powdery substance having ion exchange capacity is adjusted in accordance with the ratio of (B) metal fiber to (C) resin in the constituent materials and the type and amount of polymer flocculant. It is preferable to do.

  The metal fiber (B) that is a constituent material of the composite material composition of the present invention may be a metal fiber composed of a single metal element or an alloy fiber composed of a plurality of metals. (B) As a metal element which comprises a metal fiber, aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum, tungsten etc. are mentioned, for example.

  (B) Examples of the metal fibers include stainless steel fibers manufactured by Nippon Seisen Co., Ltd. and Bekaert Japan Co., Ltd., copper fibers manufactured by Niji Gi Co., Ltd., aluminum fibers, brass fibers, steel fibers, titanium fibers, and phosphor bronze. Although a fiber etc. can be obtained as a commercial item, it is not limited to these. These metal fibers may be used individually by 1 type, or may use 2 or more types together. Among these, copper fiber, aluminum fiber, brass fiber and the like are preferable from the viewpoint of heat dissipation, and stainless steel fiber, copper fiber, aluminum fiber and the like are preferable from the viewpoint of electromagnetic wave shielding.

(B) The metal 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 characteristics, or may be adhesive to the resin or handleability. In order to improve this, you may use what carried out the sizing agent process.

  (B) The content of the metal fiber is preferably selected according to the required requirements. For example, when workability and lightness of the resin are required, 1% by mass or more of the total content of the composite material composition is 30%. It is preferable to make it less than mass%, and when it is required that the properties of the metal and the resin are expressed in a well-balanced manner, it should be made 30 mass% or more and less than 60 mass% of the total content of the composite material composition. Preferably, when metal properties such as thermal conductivity and rigidity are required, the content is desirably 60% by mass or more and 90% by mass or less of the total content of the composite material composition. When the content of the composite material is less than 1% by mass, the lightness and workability are improved, but the effect of developing the metal performance is weak. On the other hand, when the content is more than 90% by mass of the total composite material, the material has high thermal conductivity and high rigidity, but it is not preferable because lightness and workability deteriorate.

  (B) The average fiber length of the metal fibers is desirably selected according to the required properties, and is not particularly limited, but is preferably 500 μm or more and 10 mm or less, for example. 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 properties such as thermal conductivity, electromagnetic wave shielding properties, and rigidity, 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 thus characteristics such as thermal conductivity, electromagnetic wave shielding properties, and rigidity may be difficult to develop. Further, if the average fiber length exceeds the above upper limit, it is effective for manifesting the properties of the metal, but it is not preferable because it causes a decrease in moldability. In addition, when using several metal 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.

  Depending on the required properties required, (D) fibers other than (B) fibers can be further included. (B) The fibers other than the fibers (D) 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. Fibers, polyamide fibers, aramid fibers, polyimide fibers, polyvinyl alcohol fibers, polyester fibers, acrylic fibers, polyparaphenylene benzoxazole fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, synthetic fibers such as ethylene vinyl alcohol fibers, and carbon Examples thereof include inorganic fibers such as fibers, glass 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 carbon fibers, glass fibers, ceramic fibers, and the like are preferable from the viewpoint of improving bending elastic modulus. Inorganic fibers are preferred.

  (B) Examples of fibers other than fibers (D) include Kevlar (registered trademark), which is an aramid fiber manufactured by Toray DuPont Co., Ltd., and Technora (registered trademark), which is an aramid fiber manufactured by 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., manufactured by Denki Kagaku Kogyo Co., Ltd. Dencaarcene, which is an alumina fiber, is available as a commercial product, but is not limited thereto.

(B) The shape of the fibers other than the fibers (D) can be used without any particular limitation, and those having a shape according to the required characteristics can be used. However, 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 (C) resin that is a constituent material of the composite material 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.

  (C) 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. As a result, when the polymer flocculant is added, (A) in the presence of a powdery substance having ion exchange ability, the resin and the metal fiber are liable to form an agglomerated state, and 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. In addition, the average particle diameter of (C) resin is calculated | required as a 50% particle diameter on a mass basis as an average particle diameter, for example using laser diffraction type particle size distribution measuring apparatuses, such as SALD-7000 by Shimadzu Corporation. be able to.

  The solvent used to disperse the constituent material of the composite material composition of 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 the boiling point is low. In order to remove the solvent when it is too high, it is preferable that the boiling point is 50 ° C. or more and 200 ° C. or less from the viewpoint of enormous energy, and examples of such include water, ethanol, 1-propanol. , Alcohols such as 1-butanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone, 2-heptanone and cyclohexanone, esters such as ethyl acetate, butyl acetate, methyl acetoacetate and methyl acetoacetate, tetrahydrofuran, isopropyl List ethers such as ether, dioxane, furfural, etc. It is possible. 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 material 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 material composition of the present invention has improved characteristics in addition to the above-mentioned (A) powdery substance having ion exchange capacity, (B) metal fiber, (C) resin, (D) fiber and polymer flocculant. Target inorganic powders, metal powders, stabilizers such as antioxidants and UV absorbers, mold release agents, plasticizers, flame retardants, resin curing catalysts and accelerators, pigments, dry paper strength improvers, wet paper Paper strength improvers such as strength improvers, yield improvers, freeness improvers, size fixers, antifoaming agents, rosin sizing agents for acidic papermaking, rosin sizing agents for neutral papermaking, alkyl ketene dimer sizing agents Sizing agents such as alkenyl succinic anhydride sizing agents, specially modified rosin sizing agents, coagulants such as sulfuric acid bands, aluminum chloride, polyaluminum chloride, etc. Use various additives for the purpose It is possible.

  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.

  Next, the manufacturing method of the composite material composition of this invention is demonstrated. In the composite material composition of the present invention, the constituent materials and the like are dispersed in a solvent, a polymer flocculant is added, the constituent materials and the like are aggregated in a floc form, and the aggregate is separated from the solvent. It can be obtained by removing the solvent. 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.

  Next, the manufacturing method of the molded object using the composite material composition 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 method of molding the composite material composition of the present invention by a molding method such as laminate 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 material composition (1) Reference Example 1
45 parts of a solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 2 parts bentonite (trade name Kunipia manufactured by Kunimine Industry Co., Ltd.) pulverized to an average particle size of 100 μm by an atomizer pulverizer, fiber length 5 mm, fiber diameter 1 part of 6 μm stainless fiber (trade name Naslon, manufactured by Nippon Seisen Co., Ltd.), 12 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products ( 40 parts) was added to 10,000 parts of water and 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 in advance was added. Addition of 900 ppm to the constituent material causes the constituent material to aggregate in a floc form. The agglomerates are separated from water with an 80 mesh metal mesh, after which the agglomerates are depressurized and further dried in a 70 ° C. drier for 6 hours to yield a composite composition with a 99% yield. I got it. Details of the yield measurement method will be described later.

(2) Reference example 2
45 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 5 mm, fiber diameter 4 parts of 6 μm stainless fiber (trade name Naslon manufactured by Nippon Seisen Co., Ltd.), 6 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products ( 40 parts) was added to 10,000 parts of water and 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 in advance was added. Addition of 0.3% to the constituent material causes the constituent material to aggregate in a floc form. The agglomerates are separated from water with an 80 mesh metal mesh, after which the agglomerates are depressurized and further dried in a 70 ° C. drier for 6 hours to yield a composite composition with a 99% yield. I got it.

(3) Reference example 3
30 parts of solid resol resin (PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 3 parts bentonite (trade name Kunipia manufactured by Kunimine Industries Co., Ltd.) pulverized to an average particle size of 100 μm with an atomizer pulverizer, fiber length 5 mm, fiber diameter 32 parts of 6 μm stainless fiber (trade name Naslon manufactured by Nippon Seisen Co., Ltd.), 10 parts of Kevlar (registered trademark) Pulp 1F303 (manufactured by Toray DuPont), Technora (registered trademark) fiber T32PNW (Teijin Techno Products ( Co., Ltd.) 25 parts was 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 in advance. 0.5% is added to the constituent material, and the constituent material is aggregated in a floc form. The agglomerates are separated from water with an 80 mesh metal mesh, after which the agglomerates are depressurized and dried in a 70 ° C. drier for 6 hours to yield a composite composition with a 96% yield. I got it.

(4) Example 4
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. product name Smecton SA 5 parts, fiber length 3 mm, fiber diameter 60 μm aluminum fiber (Nijigi Co., Ltd. A1070) 60 parts, cellulose pulp (Nippon Paper Chemical Co., Ltd. trade name NDPT) 10 parts Was added to 10000 parts of water, stirred with a disperser for 30 minutes, and then cationized starch SC-5 manufactured by Sanwa Starch Co., Ltd. dissolved in water in advance was 0.4% of the constituent materials. Addition is performed, and the constituent materials are aggregated in a floc form. The agglomerates are separated from water with a 40 mesh metal net, after which the agglomerates are depressurized and further placed in a dryer at 100 ° C. for 4 hours to dry, yielding a 94% yield of the composite composition. I got it.

(5) Example 5
10 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 (Shikoku Kasei Kogyo Co., Ltd.), synthetic saponite (Kunimine) 3 parts of Kogyo Co., Ltd. trade name Smecton SA), fiber length 3 mm, fiber diameter 60 μm copper fiber (Nijigi Co., Ltd.) 82 parts, cellulose pulp (Nippon Paper Chemical Co., Ltd. trade name NDPT) 4 parts Add to 10000 parts of water, stir with a disperser for 30 minutes, then add 0.3% of cationized starch SC-5 manufactured by Sanwa Starch Co., Ltd. dissolved in water to the constituent materials. And agglomerate the constituent materials in a floc form. The agglomerates are separated from water with a 40 mesh metal mesh, after which the agglomerates are depressurized and further dried in a dryer at 100 ° C. for 4 hours to yield a composite composition with a yield of 95%. Got in.

(6) Reference example 6
In a freeze pulverizer, 45 parts of pulverized acrylonitrile-styrene copolymer (AS) resin (trade name Sebian N, manufactured by Daicel Industries, Ltd.) pulverized to an average particle size of 200 μm and scaly silica particles (AGC S-Tech ( Product name Sun Lovely Co., Ltd. 5 parts, fiber length 1 mm, fiber diameter 90 μm brass fiber (manufactured by Niji Gi Co., Ltd.) 10 parts, fiber diameter 22 μm, fiber length 5 mm polyvinyl alcohol fiber (Kuraray Co., Ltd. product name) After adding 40 parts of vinylon) to 10,000 parts of water and stirring with a disperser for 30 minutes, cationic polyacrylamide (manufactured by Harima Kasei Co., Ltd.) dissolved in water in advance is 0.4 with respect to the constituent materials. Addition is performed so that the weight becomes%, and the constituent materials are aggregated in a floc form. The agglomerates are separated from water with a 40 mesh metal net, after which the agglomerates are depressurized and dried in a dryer at 130 ° C. for 6 hours to obtain a composite composition with a yield of 92%. I got it.

(7) Comparative Example 1
50 parts of a solid resol resin (PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.) pulverized to an average particle size of 100 μm by an atomizer pulverizer, and a stainless fiber having a fiber length of 5 mm and a fiber diameter of 6 μm (trade name Naslon manufactured by Nippon Seisen Co., Ltd.) ) 4 parts, 6 parts of Kevlar (registered trademark) pulp 1F303 (manufactured by Toray DuPont), 40 parts of Technora (registered trademark) fiber (manufactured by Teijin Techno Products) are added to 10,000 parts of water, After stirring with a disperser for 30 minutes, polyethylene oxide molecular weight 1,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in water in advance was added at 0.3% to the constituent materials, but agglomerated. First, it is separated from water with an 80 mesh metal mesh, then dehydrated and pressed and further placed in a 70 ° C. dryer for 6 hours to dry the composite composition. Obtained in yield.

(8) Comparative Example 2
29 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.), fiber length 3 mm, 60 parts of an aluminum fiber having a fiber diameter of 60 μm (A1070 manufactured by Niji Gi Co., Ltd.) and 10 parts of cellulose pulp (trade name NDPT manufactured by Nippon Paper Chemicals Co., Ltd.) were added to 10000 parts of water and stirred for 30 minutes with a disperser. Thereafter, a cationized starch SC-5 manufactured by Sanwa Starch Co., Ltd. previously dissolved in water was added in an amount of 0.4% by weight to the constituent material, but it did not agglomerate. The mixture was separated from water, then dehydrated and pressed, and further dried in a dryer at 100 ° C. for 4 hours to obtain a composite material composition with a yield of 82%.

2. Fabrication of molded body (1) Reference Example 7
The composite material composition obtained in Reference Example 1 was set in a mold to which a release agent was applied, and the composite material 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.

(2) Reference Example 8
The composite material composition obtained in Reference Example 2 was set in a mold coated with a release agent, and the composite material composition was compression molded 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.

(3) Reference Example 9
The composite material composition obtained in Reference Example 3 was set in a mold to which a release agent was applied, and the composite material 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 material composition obtained in Example 4 was set in a mold coated with a release agent, and compression molding was performed on the composite material composition 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.

(5) Example 11
The composite material composition obtained in Example 5 was set in a mold coated with a release agent, and the composite material composition was compression molded 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.

(6) Reference Example 12
The composite material composition obtained in Reference Example 6 was set in a mold coated with a release agent, and the composite material composition was subjected to compression molding at 200 ° C. for 10 minutes under a surface pressure of 15 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 3
The composite material composition obtained in Comparative Example 1 was set in a mold coated with a release agent, and the composite material 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.

(8) Comparative Example 4
The composite material composition obtained in Comparative Example 2 was set in a mold coated with a release agent, and the composite material composition was compression molded 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.

  The characteristic evaluation shown below was performed using the molded bodies obtained in Examples 7 to 12 and Comparative Examples 3 to 4. The results are shown in Table 1.

3. Characteristic Evaluation Method 3.1 Composite Material Composition (1) Yield Calculated by the following formula.
Yield (%) = (weight of obtained composite material composition / total weight of prepared composite material raw material) × 100
For the obtained composite material composition, the weight after drying was used, and the total weight of the prepared composite material composition raw material was the amount from which moisture was removed.

3.2 Molded body (1) Appearance of molded body For the obtained molded body, “x” indicates that the surface has molding defects such as scraping or cracks, and “o” indicates that there is no molding.

(2) Specific gravity measurement The specific gravity measurement was performed according to 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.

(3) Measurement of thermal conductivity For the measurement in the plane 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.

(4) 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.

Example 4-5 is a composite material composition obtained by the present invention. Examples 10 to 11 are molded bodies using this composite material composition.
In each of Examples 4 to 5 , the yield is good because the agglomerates are passed as compared with the composite material compositions obtained in Comparative Examples 1 and 2. In the molded body evaluation, those obtained in Examples 10 to 11 had a good yield, and thus the appearance of the molded body was not defective. In the molded products obtained in Comparative Examples 3 to 4, since the metal fibers and the resin do not form aggregates, the resin having a particle diameter smaller than the mesh size passes through the solvent during solvent removal, and the composite material composition The yield of will decrease. This resulted in a poor appearance of the molded body. When the thermal conductivity in the thickness direction of the molded product of Example 10 and Comparative Example 4 is compared, since Example 10 passes through an agglomerate for the production of the composite, metal fibers are not unevenly distributed in the molded product. The thermal conductivity in the thickness direction was 3.0 W / mK, which was 10 times or more that of ordinary plastic materials. On the other hand, in Comparative Example 4, since the composite is not passed through the agglomerate, the difference in specific gravity between the resin and the metal fiber is large and unevenly distributed in the molded body. Therefore, the thermal conductivity in the thickness direction is 0.5 W. It was a result that a difference occurred even with the same composition of / mK. Therefore, according to the present invention, it is possible to obtain a wide range of composite material compositions having an excellent balance between properties such as resin processability and light weight and properties such as metal thermal conductivity, electromagnetic wave shielding properties, and rigidity. it can.

In the present invention, it is possible to obtain a metal fiber-resin composite material composition excellent in planar isotropy with a high yield while maintaining the fiber length of the metal fiber long, and in a wider range than before, the metal fiber and the resin. The amount of resin can be adjusted, so that it has an excellent balance between properties such as resin processability and light weight, and metal thermal conductivity, electromagnetic shielding properties, and rigidity according to required requirements. A wide range of composite compositions can be obtained.
Therefore, the molded body obtained from the composite material composition of the present invention can be used for electronic products such as personal computers, mobile phones, plasma display televisions, liquid crystal televisions, lighting fixtures, internal mechanical parts of automotive electronic products, housings, etc. It can be used for structural components, structural materials for construction, automobile parts, etc., and can contribute to improvement of fuel efficiency and energy saving in weight reduction, so it is possible to reduce the environmental load. .

Claims (11)

After the constituent materials are dispersed in a solvent, a polymer flocculant is added, the constituent materials are aggregated in a floc form, the aggregate is separated from the solvent, and then the solvent is removed. A manufacturing method comprising:
The constituent materials are:
(A) a powdery substance having ion exchange capacity,
(B) metal fiber,
(C) resin,
(D) including fibrillated fibers other than metal fibers,
Content of said (B) metal fiber is 60 mass% or more and 90 mass% or less of the whole composite material composition, The manufacturing method of the composite material composition characterized by the above-mentioned. (A) The powdery substance having ion exchange ability is at least one intercalation compound selected from clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica. The manufacturing method of the composite material composition of Claim 1. 2. The composite according to claim 1, wherein (A) the powdery substance having ion exchange capacity contains at least one clay mineral selected from smectite, halloysite, kanemite, kenyanite, zirconium phosphate and titanium phosphate. A method for producing a material composition. The powdery substance having ion exchange capacity (A) contains at least one smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, soconite and stevensite. A method for producing the composite material composition described. 2. The method for producing a composite material composition according to claim 1, wherein the powdery substance (A) having ion exchange capacity contains montmorillonite. The content of the powdery substance having ion exchange capacity (A) is 0.1% by mass or more and 30% by mass or less of the entire composite material composition. The manufacturing method of the composite material composition as described in any one of. The metal element constituting the metal fiber (B) contains at least one metal element selected from aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum and tungsten. A method for producing a composite material composition according to any one of claims 1 to 6. The method for producing a composite material composition according to any one of claims 1 to 7, wherein an average fiber length of the (B) metal fiber is 500 µm or more and 10 mm or less. (D) Fibrilized fibers other than metal fibers are natural fibers such as wood fibers, cotton, hemp and wool, regenerated fibers such as rayon fibers, semi-synthetic fibers such as cellulose fibers, polyamide fibers, aramid fibers, polyimide fibers, From synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber polyparaphenylene benzoxazole fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, ethylene vinyl alcohol fiber, and inorganic fiber such as carbon fiber, glass fiber, and ceramic fiber The method for producing a composite material composition according to any one of claims 1 to 8, comprising at least one selected fiber. The method for producing a composite material composition according to any one of claims 1 to 9, wherein the resin (C) has an average particle diameter of 500 µm or less. The method for producing a composite material composition according to claim 1, wherein the solvent has a boiling point of 50 ° C. or higher and 200 ° C. or lower .