JP2015081296A - Laminate and housing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced composite material excellent in mechanical properties.SOLUTION: There is provided a fiber-reinforced composite material which is composed of a material composition comprising a fiber filler and a resin and is obtained by a papermaking method. The fiber filler has a tensile strength of 2.0 GPa or more. The filler has an average fiber length of 500 μm or more and 10 mm or less, the content of the fiber filler is 35 mass% or more and 80 mass% or less of the entire material composition and the fiber-reinforced composite material contains a powdery substance having an ion exchange capacity.

Description

  The present invention relates to a fiber-reinforced composite material and a housing.

  Fiber reinforced composite materials consisting of plastic fibers, carbon fibers, glass fibers and other reinforcing fibers and resin matrices are excellent in strength and rigidity, so they are widely used in electrical / electronic applications, civil engineering / architecture applications, automotive applications, aircraft applications, etc. It is used. Among them, a composite material using a base material in which reinforcing fibers are uniformly dispersed has isotropic mechanical properties, and furthermore, if it is a material that develops high strength, the applicable applications are greatly increased.

  As a method for producing a fiber-reinforced composite material by uniformly and isotropically dispersing reinforcing fibers, a papermaking method has been studied. For example, in Patent Document 1, a web-like molding material prepared by dispersing and making glass fiber and aramid fiber in water as a reinforcing resin and making paper is heated and pressure-molded (compression-molded) in a molding die to strengthen the fiber. Of phenolic resin molded products. Patent Document 2 discloses that glass fibers and vinylon fibers are dispersed in water together with phenol resin fine particles, and these are made and dried to obtain a sheet-like molding material, which is then heated and pressed in a mold. The production of plate-shaped molded products is described, and improvement of molded product characteristics centering on mechanical properties is being studied by selecting reinforcing fibers to be made and resin to be dispersed and mixed.

  Regarding the composite sheet produced by the papermaking method, Patent Document 3 describes a press-molded paper containing thermoplastic fibers having thermal adhesion and natural fiber elongation with natural pulp. Although a paperboard for thermoforming has been described which has a laminated structure of a paper layer mainly composed of thermoplastic fibers and a paper layer mainly composed of cellulose pulp, the molded product is good in formability although the formed sheet is good. The mechanical strength of is not high strength, and applicable applications include packaging containers for electrical and electronic parts, packaging containers for other industrial parts, packaging containers for various foods, trays, disposable tableware (lunch boxes, Folding boxes), vehicle interior materials, packaging cushioning materials, and the like.

JP 10-95024 A JP-A-10-166361 Japanese Patent Laid-Open No. 10-8393 JP 2000-265400 A

  An object of the present invention is to provide a fiber-reinforced composite material having excellent mechanical properties.

  Such an object is achieved by the present inventions [1] to [8] below.

[1] A fiber reinforced composite material composed of a material composition containing a fiber filler and a resin and obtained by a papermaking method, wherein the fiber filler has a tensile strength of 2.0 GPa or more Composite material
[2] The fiber-reinforced composite material according to [1], wherein the fiber filler has an average fiber length of 500 μm or more and 10 mm or less.
[3] The fiber-reinforced composite material according to any one of [1] or [2], wherein a content of the fiber filler is 35% by mass or more and 80% by mass or less of the entire material composition.
[4] The fiber-reinforced composite material according to any one of [1] to [3], wherein the fiber filler is an aramid fiber.
[5] The fiber-reinforced composite material according to any one of [1] to [4], wherein the material composition further includes a powdery substance having ion exchange ability.
[6] The fiber-reinforced composite material according to any one of [1] to [5], wherein the material composition further includes at least one filler powder selected from the group consisting of inorganic powder and metal powder.
[7] The fiber-reinforced composite material according to any one of [1] to [6], wherein the resin is a thermosetting resin.
[8] A housing for housing an electronic device using the fiber-reinforced composite material according to [1] to [7].

  According to the present invention, a fiber-reinforced composite material having a good appearance and excellent mechanical properties can be obtained. In particular, since a light and high-strength three-dimensional molded body can be obtained, it can be suitably used for a structure such as a casing of a portable electronic device.

 First, the fiber reinforced composite material of the present invention will be described in detail. A fiber filler having a tensile strength of 2.0 GPa or more is used for the fiber-reinforced composite material of the present invention. By using a fiber filler having a tensile strength of 2.0 GPa or more, the strength of the fiber-reinforced composite material can be improved. That is, when an impact load is applied to the surface of the fiber reinforced composite material, the fiber filler contained in the fiber reinforced composite material escapes in the surface direction, so that even if the impact load is applied, the fiber reinforced composite material It can prevent that a crack and a crack enter. As a result of intensive studies, the present inventor has found that a fiber-reinforced composite material having no practical problem can be obtained by using a fiber filler having a tensile strength of 2.0 GPa or more.

 The fiber filler having a tensile strength of 2.0 GPa is obtained by pulverizing or cutting fibers having a tensile strength of 2.0 GPa or more. Examples of fibers having a tensile strength of 2.0 GPa or more include polyamide fibers, aramid fibers, polyimide fibers, polyparaphenylene benzoxazole fibers, polyarylate fibers, ultrahigh molecular weight polyethylene fibers, synthetic fibers such as high-strength polypropylene fibers, and PAN. Examples thereof include carbon fiber, metal fiber, and inorganic fiber. The fiber filler comprised from these fibers may be used individually by 1 type, or may use 2 or more types together.

  The shape of the fiber filler can be used without any particular limitation, and a shape according to the required characteristics can be used. When improving strength characteristics such as bending strength and impact resistance, it is desirable to use chopped strands. Further, in order to obtain the yield improving effect, fibers obtained by beating a fiber with a mechanical shearing force such as a beater or a homogenizer, or fibrillated fibers are preferable. Such a fiber is preferable because it has a large fiber surface area, a physically high resin-capturing ability, and chemically easily acts with a polymer flocculant.

  Moreover, it is preferable that content of the fiber filler which concerns on this embodiment is 35 mass% or more and 80 mass% or less, and it is preferable to use properly according to the request | requirement especially calculated | required. When it is at least the above lower limit, impact resistance is improved, which is preferable. It is preferable if it is not more than the above upper limit value, since deterioration of lightness and workability can be prevented.

Further, the average fiber length of the fiber filler according to the present embodiment is not particularly limited, but it is desirable to use properly according to the required characteristics, and for example, it is preferably 500 μm or more and 10 mm or less. By setting the average fiber length to 500 μm or more, characteristics due to the fiber filler can be expressed.
On the other hand, moldability can be ensured by setting the average fiber length to 500 μm or more and 10 mm or less. The moldability means the surface smoothness and demoldability of the fiber reinforced composite material.
In particular, the average fiber length of the fiber filler is preferably 1 mm or more, more preferably 3 mm or more, and 8 mm or less from the viewpoint of exhibiting the characteristics of the fiber filler and ensuring molding processability.
The average diameter of the fiber filler is preferably 1 μm or more and 100 μm or less, and particularly preferably 5 μm or more and 80 μm or less. By setting it as 1 micrometer or more, the rigidity of a fiber reinforced composite material can be ensured, and a moldability can be ensured by setting it as 100 micrometers or less.
The length and diameter of the fiber can be confirmed, for example, by observing the obtained fiber-reinforced composite material with an electron microscope.

  For the fiber-reinforced composite material of the present invention, at least one resin selected from thermoplastic resins and thermosetting resins can be used. Such a resin is not particularly limited, and examples thereof include various thermoplastic resins and various thermosetting resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer ( EVA) and other polyolefins, cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamides (eg nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6- 12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (AB) Resin), acrylonitrile-styrene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene Polyester such as terephthalate (PBT), polycyclohexane terephthalate (PCT), polyethylene naphthalate (PEN), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene Oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), poly Trifluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyethylene, etc. Various thermoplastic elastomers, epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, urethane resins, or copolymers, blends, polymer alloys, etc. mainly composed of these. One or two or more of them can be used in combination. Since the resin is compounded with fibers and the like by wet papermaking, it is preferably in the form of particles or fibers at room temperature and insoluble in water. Among these, as the thermoplastic resin, at least one resin selected from polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyether ketone, polyether ether ketone, polysulfone, and polyphenylene sulfide is used as the molded body. It is preferable because it has a higher melting point in terms of improving heat resistance. Moreover, as a thermosetting resin, at least 1 type of resin chosen from an epoxy resin, a phenol resin, a melamine resin, and a urethane resin is especially preferable at the point which can improve the heat resistance of a molded object. 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.

  The blending amount of the resin is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and particularly preferably 20 to 50% by mass with respect to the entire fiber reinforced composite material. Thereby, when a fiber reinforced composite material is heat-press molded, it is possible to produce a molded body having a good appearance and less resin uneven distribution.

  Examples of the surface treatment of the fiber filler include a coupling treatment with a surface treatment agent. The surface treatment agent is not particularly limited as long as it is a surface treatment agent having an interfacial adhesive strength within the above range when applied to the fiber filler, and a known one can be used. Specifically, one or more coupling agents selected from an epoxy silane coupling agent, a cationic silane coupling agent, an amino silane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent should be used. Can do.

When using the fiber filler, a powdery substance having ion exchange ability may be further included. By using such a powder material having ion exchange capacity, it is possible to efficiently produce an aggregate of the fiber filler and the resin with a high yield while keeping the fiber length of the fiber filler long. It becomes possible to adjust the compounding ratio of the filler and the resin over a wide range. For this reason, according to the request | requirement calculated | required, the wide fiber reinforced composite material excellent in the balance of the characteristic of a fiber filler and the characteristic of resin can be obtained more efficiently.
The powdery substance having ion exchange capacity preferably contains 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 even if it is a natural product or a synthesized one, 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, lithium tetrasilicon fluorine, and the like. Or you may use 2 or more types together.
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.
Examples of powdery substances having ion exchange capacity include Kunipia (bentonite) manufactured by Kunimine Kogyo Co., Ltd., Smecton SA (synthetic saponite), Sunlabry (scale-like silica fine particles) manufactured by AGC S-Itech Co., Ltd., Corp Chemical Somasif (swelling synthetic mica), Lucentite (synthetic smectite) manufactured by Co., Ltd., Hydrotalcite STABACE HT-1 (hydrotalcite) manufactured by Sakai Chemical Industry Co., Ltd. are commercially available. However, it is not limited to these.

  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 fiber reinforced composite material. If it is in the said range, the effect of improving the workability | operativity of the structural material from which a property differs like a fiber filler and resin can be acquired. In addition, it is preferable to adjust the content of the powdery substance having ion exchange capacity according to the ratio between the fiber filler and the resin, the type and amount of the polymer flocculant, and the like.

 The fiber reinforced composite material preferably contains a polymer flocculant. Although the polymer flocculant is mentioned later in detail, it is for aggregating a fiber filler and resin in the shape of a flock. The polymer flocculant is not particularly limited by ionicity, and cationic polymer flocculants, anionic polymer flocculants, nonionic polymer flocculants, amphoteric polymer flocculants 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 Chemical Co., Ltd. Halifix, 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. However, it is not limited to these.

  The amount of the polymer flocculant added is not particularly limited, but is preferably 100 mass ppm or more and 1 mass% or less with respect to the entire fiber-reinforced composite 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 fiber-reinforced composite material of the present invention can be adjusted in characteristics by further containing 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 fiber reinforced composite material has improved properties in addition to the above-mentioned fiber filler, resin, powdery substance having ion exchange ability, at least one filler powder selected from inorganic powder and metal powder, and polymer flocculant. Objective stabilizers such as antioxidants and UV absorbers, release agents, plasticizers, flame retardants, resin curing catalysts and accelerators, pigments, dry paper strength improvers, wet paper strength improvers and other paper Strength improver, yield improver, freeness improver, size fixer, antifoaming agent, rosin sizing agent for acidic papermaking, rosin sizing agent for neutral papermaking, alkyl ketene dimer sizing agent, alkenyl succinic anhydride Aiming to adjust production conditions and develop the required physical properties of sizing agents such as sizing agents, specially modified rosin sizing agents, and coagulants such as sulfate bands, aluminum chloride, and polyaluminum chloride. It may be used various additives.

  The fiber-reinforced composite material according to this embodiment is obtained by a papermaking method. Here, the papermaking method indicates a papermaking technique which is one of papermaking techniques. According to this embodiment, the material composition containing the fiber filler and resin obtained using this technique is used. By doing so, a high-strength fiber-reinforced composite material can be obtained. Although this reason is not necessarily clear, it is thought that it is because the entanglement of fiber fillers can be made.

The fiber-reinforced composite material according to the present embodiment is manufactured by a papermaking method. Examples of the manufacturing method include the following examples. Among the constituent materials of the fiber reinforced composite material described above, the material excluding the polymer flocculant is added to the solvent, and is stirred and dispersed. A method of dispersing the material in a solvent is not particularly limited, and examples thereof include a method of stirring with a disperser or a homogenizer.

The solvent is not particularly limited, but in the process of dispersing the constituent material of the fiber reinforced composite material, it is difficult to volatilize, and since it does not remain in the fiber reinforced composite material, it is easy to remove the solvent, and the boiling point is too high. In order to remove the solvent, those having a boiling point of 50 ° C. or higher and 200 ° C. or lower are preferable from the viewpoint of enormous energy, and examples of such include water, ethanol, 1-propanol, 1 -Alcohols such as butanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone, 2-heptanone and cyclohexanone, esters such as ethyl acetate, butyl acetate and methyl acetoacetate, tetrahydrofuran, isopropyl ether, dioxane, furfural, etc. Of 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.

  Thereafter, a polymer flocculant is added. When the fiber reinforced composite material has a powdery substance having ion exchange ability, the powdery substance having ion exchange ability makes it easy for the resin and the fiber filler to form an agglomerated state, and the constituent material in the solvent is floc-like. Furthermore, it becomes easier to aggregate.

  Thereafter, the solvent and the agglomerated constituent material (aggregate) are placed in a container having a bottom made of mesh, and the solvent is discharged from the mesh. Thereby, an aggregate and a solvent will be isolate | separated (papermaking process). Next, the sheet-like aggregate is taken out from the container, and the aggregate is put into a drying furnace and dried to further remove the solvent. Thereafter, the aggregate is formed. Thereby, a fiber reinforced composite material is obtained. Examples of the molding method include molding methods such as press molding, compression molding, calender roll molding, SMC method, injection molding, matched die method, laminate molding with resin, woven fabric, nonwoven fabric and the like.

  The fiber-reinforced composite material of the present invention can be widely used in electrical / electronic applications, civil engineering / architecture applications, automobile applications, aircraft applications, and the like. Specifically, for example, it can be used for various members in housings for electronic devices and the like, building materials for houses and furniture, vehicles, aircrafts, and the like. The fiber-reinforced composite material of the present invention can be easily molded into a free shape, imparting appropriate characteristics depending on the application.

(1) Example 1
50 parts of an average 30 μm phenol resin (product number PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.), 40 parts of aramid fiber filler (product number: T32PNW, manufactured by Teijin Limited) having a fiber diameter of 12 μm, and aramid fiber pulp (product number: manufactured by DuPont) 5 parts of aramid alp) and 5 parts of hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., product number STABIACE HT-1) were added to 10,000 parts of water, followed by stirring with a disperser for 20 minutes.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(2) Example 2
Except for 40 parts of an average 30 μm phenol resin (product number PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 50 parts of an aramid fiber filler (product number T32PNW manufactured by Teijin Limited) having a fiber diameter of 12 μm and a length of 3 mm, the same as in Example 1. A molded body was obtained.

(3) Example 3
Except for 40 parts of an average 30 μm phenol resin (product number PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 50 parts of an aramid fiber filler (product number T32PNW manufactured by Teijin Limited) having a fiber diameter of 12 μm and a length of 3 mm, the same as in Example 1. A molded body was obtained.

(4) Example 4
40 parts of an average 30 μm phenol resin (product number PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.), 50 parts of a PBO fiber filler (product number: Zylon, manufactured by Toyobo Co., Ltd.) having a fiber diameter of 10 μm and a length of 3 mm, and aramid fiber pulp (product number para, manufactured by DuPont) 5 parts of aramid alp) and 5 parts of hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., product number STABIACE HT-1) were added to 10,000 parts of water, followed by stirring with a disperser for 20 minutes.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(5) Example 5
40 parts of an average 30 μm phenol resin (product number PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.), 50 parts of E glass fiber (product number CS3J-888 manufactured by Nittobo Co., Ltd.) having a fiber length of 3 mm and a fiber diameter of 12 μm, and an aramid fiber pulp (DuPont) 5 parts of product number para-aramid alp) and 5 parts of hydrotalcite (product number STABIOCE HT-1 manufactured by Sakai Chemical Industry Co., Ltd.) were added to 10,000 parts of water and stirred for 20 minutes with a disperser.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(6) Example 6
40 parts of an average 30 μm phenol resin (product number PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.), 50 parts of PAN-based carbon fiber (product number trading card T008-003, manufactured by Toray Industries Inc.) having a fiber length of 3 mm and a fiber diameter of 7 μm, and an aramid fiber pulp (DuPont) 5 parts of a product No. Para-aramid Alp (product name) and 5 parts of hydrotalcite (Product No. STABIACE HT-1 manufactured by Sakai Chemical Industry Co., Ltd.) were added to 10,000 parts of water and stirred for 20 minutes with a disperser.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(7) Example 7
35 parts of an average 30 μm phenol resin (product number PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.), 40 parts of aramid fiber filler (product number: T32PNW, manufactured by Teijin Limited) having a fiber diameter of 12 μm, and aramid fiber pulp (manufactured by DuPont, product number para) 5 parts of aramid alp), 5 parts of hydrotalcite (product number STABIOCE HT-1 manufactured by Sakai Chemical Industry Co., Ltd.) and 5 parts of alumina (product number AM-27 manufactured by Sumitomo Chemical Co., Ltd.) are added to 10,000 parts of water, and 20 parts are added with a disperser. Stir for minutes.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(8) Comparative Example 1
50 parts of an average 30 μm phenol resin (product number PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.), 40 parts of nylon fiber filler (product number 6D-2MM, manufactured by Chubu Pile Co., Ltd.) having a fiber diameter of 6 μm and a length of 3 mm, and aramid fiber pulp (DuPont) 5 parts of product number para-aramid alp) and 5 parts of hydrotalcite (product number STABIOCE HT-1 manufactured by Sakai Chemical Industry Co., Ltd.) were added to 10,000 parts of water and stirred for 20 minutes with a disperser.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(9) Comparative Example 2
Comparative Example 1 except that 30 parts of an average 30 μm phenol resin (product number PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.) and 60 parts of a nylon fiber filler (product number 6D-2MM manufactured by Chubu Pile Co., Ltd.) having a fiber diameter of 6 μm and a length of 3 mm were used. In the same manner, a molded body was obtained.

(10) Comparative Example 3
50 parts of an average 30 μm phenol resin (product number PR-51723 manufactured by Sumitomo Bakelite Co., Ltd.), 40 parts of a pitch-based carbon fiber filler (product number K223Y1 manufactured by Mitsubishi Plastics) having a fiber diameter of 6 μm and a length of 3 mm, and aramid fiber pulp (manufactured by DuPont) 5 parts of product number para-aramid alp) and 5 parts of hydrotalcite (product number STABIACE HT-1 manufactured by Sakai Chemical Industry Co., Ltd.) were added to 10,000 parts of water and stirred for 20 minutes with a disperser.
Next, a flocculant (polyethylene oxide, molecular weight 1,000,000) dissolved in water in advance was added in an amount of 0.5% to the constituent materials, and agglomerated in a floc form.
This was filtered through a 40-mesh metal mesh, the agglomerate was dehydrated and pressed at a pressure of 3 Pa, and then dried at 50 ° C. for 5 hours to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

(11) Comparative Example 4
50 parts of an average 30 μm phenol resin (manufactured by Sumitomo Bakelite, product number PR-51723), hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., product number STABIACE HT-1), 45 parts of alumina (manufactured by Sumitomo Chemical product number AM-27) The mixture was kneaded with a pressure kneader at a temperature of 100 ° C. for 40 minutes to obtain a kneaded product. The kneaded product was compressed to a thickness of several tens of mm with a hydraulic press, and further passed through a metal roll at 80 ° C. several times to cut off the end portion to obtain a sheet-like compound.
This sheet-like compound was cured at 180 ° C. for 10 minutes at a pressure of 30 MPa to obtain a molded body of 10 cm × 10 cm × 1 mm.

Using the molded bodies obtained in Examples 1 to 7 and Comparative Examples 1 to 4, the following characteristic evaluation was performed. The results are shown in Table 1.

(1) Bending strength and flexural modulus Bending strength and flexural modulus were performed in accordance with JIS K 6911. The test piece used was cut out to 2.5 cm × 5 cm from the laminates obtained from the examples and comparative examples. The measurement was performed by a three-point bending test method.

(2) Linear expansion coefficient The linear expansion coefficient was measured by the TMA method. The test piece was cut out from the laminates obtained from the examples and comparative examples so as to be 1 cm × 4 cm, and the heating rate was 10 ° C./min.

(3) DuPont impact test The DuPont impact test was conducted in accordance with JIS K 5600-5-3. The test piece used was cut out from the laminates obtained from Examples and Comparative Examples so as to be 5 cm × 5 cm × 1 mm. The equipment used was IM-4520 manufactured by Ueshima Seisakusho Co., Ltd., the weight of the weight was 300 g, the weight was dropped at 15 cm to 50 cm.

  Examples 1 to 7 were all laminates excellent in the DuPont impact test. On the other hand, in Comparative Examples 1-4, since the fiber filler whose tensile strength of a fiber filler was 2.0 GPa or more was not used, the laminated body which was excellent in the DuPont impact test was not able to be obtained.

Claims (8)

  A fiber-reinforced composite material, which is composed of a material composition containing a fiber filler and a resin and is obtained by a papermaking method, wherein the fiber filler has a tensile strength of 2.0 GPa or more.   The fiber-reinforced composite material according to claim 1, wherein an average fiber length of the fiber filler is 500 µm or more and 10 mm or less.   The fiber-reinforced composite material according to any one of claims 1 and 2, wherein a content of the fiber filler is 35% by mass or more and 80% by mass or less of the entire material composition.   The fiber-reinforced composite material according to any one of claims 1 to 3, wherein the fiber filler is an aramid fiber.   The fiber reinforced composite material according to any one of claims 1 to 4, wherein the material composition further includes a powdery substance having ion exchange ability.   The fiber-reinforced composite material according to any one of claims 1 to 5, wherein the material composition further includes at least one filler powder selected from the group consisting of inorganic powder and metal powder.   The fiber-reinforced composite material according to any one of claims 1 to 6, wherein the resin is a thermosetting resin.   A housing that houses an electronic device using the fiber-reinforced composite material according to claim 1.