WO2021215162A1

WO2021215162A1 - Fiber-reinforced resin composite sheet, fiber-reinforced resin composite material, and molded resin article including same

Info

Publication number: WO2021215162A1
Application number: PCT/JP2021/011452
Authority: WO
Inventors: 尚哲金森; 秀和兼岩; 敬洋長谷川; 結中野; 史織佐藤
Original assignee: フクビ化学工業株式会社
Priority date: 2020-04-21
Filing date: 2021-03-19
Publication date: 2021-10-28
Also published as: CN115397641A; JPWO2021215162A1

Abstract

Provided is a fiber-reinforced resin composite sheet that has excellent flame retardant properties, that has favorable moldability, and that has sufficient tensile strength in high temperature conditions. The fiber-reinforced resin composite sheet includes a flame-retardant resin film which is made from a thermoplastic resin composition that has a glass transition temperature Tg of not less than 90°C, and a plurality of reinforcement fibers which are from an opened reinforcement fiber bundle and which are laminated in the flame-retardant resin film so as to be aligned along the same direction. The flammability category of the flame-retardant resin film as determined by the UL94VTM flammability test according to the ASTM D4804 standard is VTM-0. The volume content Vf of the reinforcement fibers is 30-65%. The thickness of the fiber-reinforced resin composite sheet is 20-100 μm. The flammability category of the fiber-reinforced resin composite sheet as determined by the UL94-5V flammability test according to the ASTM D5048 standard is 5V-A or 5V-B.

Description

Fiber reinforced resin composite sheet, fiber reinforced resin composite material and resin molded products provided with it

The present invention relates to a fiber-reinforced resin composite sheet containing a flame-retardant resin film and reinforcing fibers.

Fiber reinforced resin composite materials are widely used materials from parts for sports and leisure use to parts for industrial use such as automobiles and aircraft. Further, the fiber-reinforced resin composite material is manufactured by using an intermediate material, that is, a prepreg, in which a reinforcing material made of long fibers (continuous fibers) such as reinforcing fibers is impregnated into a resin matrix. Specifically, a molded product of a fiber-reinforced resin composite material can be obtained by laminating a plurality of prepregs and heating and curing them, or by heating and cooling to solidify them.

Conventionally, thermosetting resins have been often used as resins used for prepregs from the viewpoint of excellent strength and rigidity in the production of fiber-reinforced resin composite materials (see, for example, Patent Document 1). However, the prepreg using the thermosetting resin has a problem that the impact resistance is low and the secondary processability is difficult. In order to solve these problems, a prepreg in which a matrix resin is impregnated with reinforcing fibers using a thermoplastic resin has been widely developed. According to such a prepreg, since it is easy to melt by heating and solidify by cooling, it is excellent in operability at the time of molding the prepreg, and it is expected to have an effect of shortening the production time, which leads to cost reduction.

Recently, fiber-reinforced resin composite materials have also been used as materials for housings and parts of smartphones, tablets, notebook computers, video cameras, mobile devices, and other electrical or electronic devices. When the housing or parts of an electric device or electronic device is exposed to heat generated from the inside of the device or in a high temperature environment, the housing or parts may ignite and burn. In order to prevent such accidents, the material prepreg is required to be flame retardant. In general, thermosetting resins are excellent in flame retardancy, but thermoplastic resins are inferior in flame retardancy, and thermoplastic resins having sufficient flame retardancy by themselves without adding a flame retardant are There are few (see, for example, Patent Document 2). Therefore, when producing a fiber-reinforced resin composite material that requires flame retardancy, a thermosetting resin is mainly used as the matrix resin.

However, depending on the type of molded product, for example, the type of housing or parts of electrical equipment or electronic equipment, in order to increase the degree of freedom in shape, it is also referred to as a fiber reinforced resin composite material (hereinafter, "fiber reinforced resin composite sheet"). In some cases, good molding processability is required. On the other hand, a fiber-reinforced resin composite sheet using a thermoplastic resin as a matrix resin is superior in moldability to a fiber-reinforced resin composite sheet using a thermosetting resin, but has a problem of being inferior in strength. .. Depending on the type of housing, parts, etc. of the electric device or electronic device as described above, strength, for example, tensile strength may also be required.

Japanese Unexamined Patent Publication No. 8-118381 Japanese Unexamined Patent Publication No. 2005-239939

Therefore, an object of the present invention is to provide a fiber reinforced resin composite sheet having excellent flame retardancy, good molding processability, and sufficient tensile strength under high temperature conditions.

The fiber-reinforced resin composite sheet according to the first aspect of the present invention comprises a flame-retardant resin film made of a thermoplastic resin composition having a glass transition temperature Tg of 90 ° C. or higher, and a reinforced fiber bundle formed on the flame-retardant resin film. It is a fiber reinforced resin composite sheet containing a plurality of reinforcing fibers laminated in a state in which a plurality of reinforcing fibers opened from the above are oriented in the same direction.
The flammability classification of the flame-retardant resin film determined in the UL94 VTM combustion test conforming to the ASTM D4804 standard is VTM-0.
The volume content Vf of the reinforcing fiber is 30% or more and 65% or less.
The thickness of the fiber reinforced resin composite sheet is 20 μm or more and 100 μm or less.
The combustibility classification of the fiber reinforced resin composite sheet determined in the UL94-5V combustion test conforming to the ASTM D5048 standard is 5VA or 5V-B.

FIG. 1 is a diagram showing an example of a schematic configuration of a fiber-reinforced resin composite sheet manufacturing apparatus according to the present embodiment. FIG. 2 is a diagram showing an example of a method of cutting out a chop material from a fiber reinforced resin composite sheet in the present embodiment. FIG. 3 is a diagram for explaining a method for producing a laminated chopped sheet, which is an example of the fiber reinforced resin composite material in the present embodiment. FIG. 4 is a cross-sectional view of a laminated chopped sheet which is an example of the fiber reinforced resin composite material in the present embodiment. FIG. 5 is a laser microscope image of a cross section of a test piece of a fiber reinforced resin composite sheet in Example 2-1 and Example 2-2 and Comparative Example 2-1 and Comparative Example 2-2. FIG. 6 is an image showing the results of a flame-retardant additional test of the test pieces of the fiber-reinforced resin composite sheet in Example 2-1 and Example 2-2 and Comparative Example 2-1 and Comparative Example 2-2.

The larger the volume content Vf of the reinforcing fiber in the fiber-reinforced resin composite material, the larger the tensile strength of the fiber-reinforced resin composite material tends to be. However, when the fiber-reinforced resin composite sheet, which is an intermediate material, is manufactured, the sheet becomes thicker just by increasing the amount of the reinforcing fibers impregnated in the resin matrix, and the moldability of the fiber-reinforced resin composite sheet deteriorates. It ends up. Furthermore, it is predicted that the structure of the reinforcing fibers, the value of the volume content Vf, and the like will affect the flame retardancy of the fiber reinforced resin composite sheet and the like. As described above, in the fiber reinforced resin composite sheet using the thermoplastic resin, it is difficult to adjust so that the characteristics of flame retardancy, moldability and strength are all suitable.

Further, when a thermoplastic resin is used as the matrix resin, the polyamide 6 resin may be used from the viewpoint of excellent physical properties such as impact resistance, toughness and flexibility, as well as from the viewpoint of cost and ease of handling. many. However, since the polyamide 6 resin has a relatively low glass transition temperature Tg, the strength of the fiber-reinforced resin composite sheet produced using the polyamide 6 resin may decrease under high temperature conditions. Therefore, the polyamide 6 resin is not suitable as a material that may be exposed to heat from the inside of the housing or parts of an electric device or an electronic device.

Therefore, the present inventors have diligently studied a fiber-reinforced resin composite sheet having excellent flame retardancy, good molding processability, and sufficient tensile strength under high temperature conditions. As a result, the present invention has been reached. Specifically, a composition of a thermoplastic resin having a predetermined property is selected, a fiber-reinforced resin composite sheet having a predetermined structure is formed, and the type and amount of the flame retardant to be optionally added are appropriately selected. The fiber-reinforced resin composite sheet as described above can be provided by setting and appropriately adjusting the volume content Vf of the reinforcing fibers within a predetermined range.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

<Fiber reinforced plastic composite sheet>
The fiber-reinforced resin composite sheet in the present embodiment includes a flame-retardant resin film and a plurality of reinforcing fibers laminated on the flame-retardant resin film. The plurality of reinforcing fibers are laminated on a flame-retardant resin film in a state in which a plurality of reinforcing fibers opened from the reinforcing fiber bundle are oriented in the same direction.

Here, in the entire specification, "reinforcing fibers are laminated" used in the "flame-retardant resin film" means a treatment performed for the physical property value, shape, and lamination of the flame-retardant resin film. "Reinforcing fibers are laminated on the flame-retardant resin film at least in part" and "Reinforcing fibers adhere to the flame-retardant resin film in at least part" depending on the type and conditions thereof. "The reinforcing fibers are laminated after being pressure-bonded to the flame-retardant resin film at least in part" and "The reinforcing fibers are laminated after being pressure-bonded to the flame-retardant resin film" and "The reinforcing fibers are laminated in about half of each reinforcing fiber. It also includes the meaning of "it is in a state of being impregnated from the surface to the inside". More specifically, at the time of "lamination", heating, cooling and / or pressure treatment may be performed as necessary.

First, each component included in the fiber-reinforced resin composite sheet in the present embodiment will be described.

[Flame-retardant resin film]
The flame-retardant resin film comprises a thermoplastic resin composition having a glass transition temperature Tg of 90 ° C. or higher. When the thermoplastic resin contained in the thermoplastic resin composition has flame-retardant properties, the thermoplastic resin composition may consist of the thermoplastic resin alone. Alternatively, if the thermoplastic resin contained in the thermoplastic resin composition does not have flame retardant properties, the thermoplastic resin composition contains a flame retardant. Further, the thermoplastic resin composition may contain additives other than the flame retardant, if necessary. Hereinafter, each component contained in the thermoplastic resin composition will be described.

(Thermoplastic resin)
The thermoplastic resin composition is not particularly limited as long as the glass transition temperature Tg is 90 ° C. or higher, and may consist of the thermoplastic resin alone, or may be a composition containing the thermoplastic resin and a flame retardant. good. Alternatively, a commercially available product can also be used. Examples of the type of thermoplastic resin include methacrylic resin such as polymethylmethacrylate resin, polystyrene resin, ABS resin, polystyrene resin such as AS resin, polyamide (PA) resin such as PA9T, polycarbonate (PC) resin, and polyphenylene. Sulfide (PPS) resin, modified polyphenylene ether (PPE) resin, polyetherimide (PEI) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, polyarylate (PAR) resin, polyethernitrile (PEN) resin , Polyetherketone (PEK) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, polyimide (PI) resin, polyamideimide (PAI) resin, fluorine (F) resin; liquid crystal polyester resin, etc. The liquid crystal polymer (LCP) resin of the above, or a copolymer resin or a modified resin thereof and the like can be mentioned. These thermoplastic resins may be contained alone or in combination in the thermoplastic resin composition.

Among these thermoplastic resins, it is preferable to use a highly heat-resistant plastic resin, so-called super engineering plastic, from the viewpoint of being excellent in various properties such as heat resistance, flame retardancy and strength. That is, the thermoplastic resin composition is preferably a polyphenylene sulfide (PPS) resin, a polyetheretherketone (PEEK) resin, a polyetherketoneketone (PEKK) resin, a polyetherimide (PEI) resin, or a polyethersulfone (PES). ) Includes one or more selected from resins and liquid crystal polymer (LCP) resins. Since these thermoplastic resins have excellent flame retardant properties, the thermoplastic resin composition may consist of these thermoplastic resins alone. Specifically, if these resin films satisfy the conditions of the flammability classification described later, and the fiber-reinforced resin composite sheet produced using the resin film also satisfies the conditions of the flammability classification described later, the flame retardant is used. It does not have to be included. Further, among these superempuras, from the viewpoint of having a high continuous use temperature, the thermoplastic resin composition is a polyphenylene sulfide (PPS) resin, a polyetheretherketone (PEEK) resin, and a polyetherketoneketone (PEKK) resin. It is more preferable to include one or more selected from. For example, a flame-retardant resin film made of a thermoplastic resin composition comprises any one of a polyphenylene sulfide (PPS) resin, a polyetheretherketone (PEEK) resin, and a polyetherketoneketone (PEKK) resin. May be.

For these super engineering plastics, known commercially available products may be used. Commercially available products of polyphenylene sulfide (PPS) resin include, for example, Toray's "Trelina (registered trademark)", Polyplastics' "Durafide (registered trademark)", and Solvay's "Ryton (registered trademark)". , Etc. can be mentioned. Commercially available products of polyetheretherketone (PEEK) resin include, for example, "TORAY TPS (registered trademark) PEEK" manufactured by Toray Industries, "Vestakeep" manufactured by Daicel Ebonic, and "PEEK polymer" manufactured by Victrex. Can be mentioned. Examples of commercially available products of the polyetherketoneketone (PEKK) resin include "Kepstan (registered trademark) PEKK" manufactured by Arkema. Examples of commercially available polyetherimide (PEI) resins include "Ultem (registered trademark)" manufactured by Sabic. Commercially available products of polyether sulfone (PES) resin include, for example, "Sumika Excel PES" manufactured by Sumitomo Chemical Co., Ltd., "Mitsui PES (registered trademark)" manufactured by Mitsui Chemical Fine Co., Ltd., and "Ultrazone (registered)" manufactured by BASF. Trademark) E ”and the like. Commercially available liquid crystal polymer (LCP) resins include, for example, "Sumika Super LCP" manufactured by Sumitomo Chemical Co., Ltd., "Laperos (registered trademark) LCP" manufactured by Polyplastics Co., Ltd., and "UENOLCP (registered)" manufactured by Ueno Junyaku Co., Ltd. Trademark) ”and the like.

Alternatively, the thermoplastic resin composition preferably contains a polycarbonate (PC) resin from the viewpoint of obtaining a fiber-reinforced resin composite sheet having excellent processability. When the thermoplastic resin composition contains a polycarbonate (PC) resin as the thermoplastic resin, the thermoplastic resin composition is selected from a halogen-based flame retardant, a phosphorus-based flame retardant, a silicone-based flame retardant, and an inorganic flame retardant. It is preferable to further contain one or more flame retardants.

In the present embodiment, since the glass transition temperature Tg of the thermoplastic resin composition constituting the flame-retardant resin film is 90 ° C. or higher, the fiber-reinforced resin composite sheet or the like produced by using the thermoplastic resin composition is It is expected that properties such as tensile strength and bending strength will not deteriorate even under high temperature conditions. On the other hand, for example, the glass transition temperature Tg of the polyamide 6 resin matrix widely used as the resin matrix of the prepreg is about 50 ° C. (see Comparative Example 1-1 described later). Therefore, it is predicted that the fiber-reinforced resin composite sheet or the like produced by using the polyamide 6 resin will have reduced properties such as strength under high temperature conditions.

(Flame retardants)
The thermoplastic resin composition contains a flame retardant, if necessary. In particular, when the thermoplastic resin contained in the thermoplastic resin composition does not have flame retardant properties, the thermoplastic resin composition contains a flame retardant as an essential component. Even when the thermoplastic resin contained in the thermoplastic resin composition has flame-retardant properties, a flame retardant may be further contained from the viewpoint of improving the flame-retardant properties.

The flame retardant is not particularly limited, and examples thereof include halogen-based flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and other flame retardants. Each will be described below.

Examples of the halogen-based flame retardant include a bromine-based flame retardant and a chlorine-based flame retardant.

Examples of the brominated flame retardant include decabromodiphenyl ether; tetrabromobisphenol A, derivatives thereof, tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol A epoxy oligomer, etc.; polybenzene ring compound-based bis (pentabromophenyl) ethane. , 1,2-bis (2,4,6-tribromophenoxy) ethane, etc .; brominated polystyrene-based brominated polystyrene, polybrominated styrene, etc .; Group hexabromocyclododecane and the like; or other hexabromobenzene, pentabromobenzyl acrylate and the like can be mentioned. Examples of the chlorine-based flame retardant include chlorinated paraffin, declorane, chlorendic acid, and chlorendic anhydride.

Examples of phosphorus-based flame retardants include aromatic phosphate ester-based flame retardants, aromatic condensation-type phosphoric acid ester-based flame retardants, halogen-containing phosphoric acid ester-based flame retardants, and other phosphorus-based flame retardants.

Examples of the aromatic phosphoric acid ester flame retardant include triphenyl phosphate, cresylphenyl phosphate, tricresyl phosphate, trixilinyl phosphate, tris (t-butylated phenyl) phosphate, and tris (i). -Phenyl propylated) phosphate, 2-ethylhexyldiphenyl phosphate and the like can be mentioned. Examples of the aromatic condensed phosphoric acid ester flame retardant include 1,3 phenylenebis (diphenylphosphate) and 1,2phenylenbis (dixylenyl phosphate). Examples of the halogen-containing phosphoric acid ester flame retardant include tris (dichloropropyl) phosphate, trischloroethyl phosphate, 2,2 bis (dichloromethyl) trimethylene, and bis (2-chloroethyl) phosphate. Examples of other phosphorus-based flame retardants include red phosphorus, phosphate ester amide, and ammonium polyphosphate.

Examples of the silicone-based flame retardant include polydimethylsiloxane, polymethylethylsiloxane, polymethyloctylsiloxane, polymethylvinylsiloxane, polydimethylphenylsiloxane, polydiphenylsiloxane, polydimethyldiphenylsiloxane, and polymethyl (3,3,3-). Trifluoropropyl) siloxane and the like.

Examples of the inorganic flame retardant include antimony compounds such as antimony trioxide, antimony tetroxide, antimony tetroxide, and sodium antimonate; molybdenum compounds such as molybdenum oxide and ammon molybdenate; water such as aluminum hydroxide and magnesium hydroxide. Japanese metal compounds; nanofillers such as titanium oxide, montmorillonite, silica; or zinc borate, zinc tinate, zinc sulfide, tin oxide, zirconium oxide, zeolite, low melting point glass and the like can be mentioned.

Other flame retardants include, for example, melamine compounds such as melamine cyanurate and melamine sulfate, nitrogen compounds such as triazine compounds and guanidine compounds; calcium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, potassium diphenylsulphonate, diphenyl. Organic metal compounds such as potassium sulphon-3-sulphonate and potassium p-toluene sulphonate; or hindered amine compounds, expansive graphite and the like can be mentioned.

Among the above-mentioned flame retardants, halogen-based flame retardants, phosphorus-based flame retardants, hindered amine compounds and antimony compounds have flame retardancy due to radical trapping action. Further, the hydrated metal compound and the expandable graphite have flame retardancy due to the endothermic action. Phosphorus-based flame retardants, halogen-based flame retardants, nitrogen compounds, hydrated metal compounds, antimony compounds and ammonium polyphosphate have flame retardancy due to oxygen blocking action or flammable gas dilution action. Silicone flame retardants, low melting point glass, hydrated metal compounds, red phosphorus, ammonium polyphosphate, expansive graphite and organic metal compounds have flame retardancy due to heat insulating action. By combining flame retardants having different actions so as to have a desired flame retardant action, a thermoplastic resin composition having a desired flame retardant action can be obtained.

The flame retardant is suitable in the thermoplastic resin composition so that the flame retardant resin film made of the thermoplastic resin composition becomes VTM-0 in the flammability classification determined in the UL94 VTM combustion test conforming to the ASTM D4804 standard. The amount may be adjusted and included. The UL94 VTM combustion test conforming to the ASTM D4804 standard will be described in detail in Examples described later. Further, as the flame retardant, the value of the volume content Vf of the reinforcing fiber is taken into consideration so that the fiber-reinforced resin composite sheet manufactured by using the flame-retardant resin film also satisfies the conditions of the flammability classification described later. It is necessary to adjust the addition amount and include it.

Specifically, for example, in the thermoplastic resin composition, the flame retardant may be contained in an amount of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. Alternatively, as described above, if the thermoplastic resin itself contained in the thermoplastic resin composition has suitable flame retardant properties, the flame retardant may not be contained.

(Other additives)
If necessary, the thermoplastic resin composition may contain various known additives as long as the effects of the present invention are not impaired. For example, in order to improve the storage stability of the thermoplastic resin composition and avoid discoloration or alteration of the solidified product, an antioxidant, a light stabilizer, a weather resistance improving material and the like can be added.

Specific other additives include, for example, thermosetting polymers, thermoplastic elastomers, silicone oils, wet dispersants, defoamers, defoamers, natural waxes, synthetic waxes, and metal salts of linear fatty acids. , Acid amides, esters, defoamers such as paraffins, crystalline silica, molten silica, calcium silicate, alumina, calcium carbonate, talc, barium sulfate and other powders, metal oxides, metal hydroxides, glass Inorganic fillers such as fibers, carbon nanotubes and fullerene, organic fillers such as carbon fibers and cellulose nanofibers, colorants such as red iron oxide, silane coupling agents, conductive materials, slip agents, leveling agents, polymerization inhibitors such as hydroquinone monomethyl ethers. , UV absorber and the like. These additives may be used alone or in combination of two or more as appropriate.

Further, the flame-retardant resin film made of the thermoplastic resin composition can be produced by applying any method known to those skilled in the art. The method for producing the film is not particularly limited, and examples thereof include a roll coating, a reverse coating, a comma coating, a knife coating, a die coating, a gravure coating, a melt extrusion method, a solution casting method, a T die method, and a calendar method. Be done. Further, by using the coextrusion method or the laminating method, it is possible to increase the thickness or to laminate resin films having different resin compositions.

The lower limit of the thickness of the flame-retardant resin film is not particularly limited, but preferably 5 μm or more, it is easy to maintain the morphology of the film well at the time of film molding. The thickness of the flame-retardant resin film is preferably 50 μm or less, more preferably 45 μm or less, still more preferably 40 μm or less, still more preferably 30 μm or less, 25 μm or less, or 20 μm or less. By setting the thickness of the flame-retardant resin film to 50 μm or less, the fiber-reinforced resin composite sheet in the present embodiment can also be made thin, and as a result, good molding processability can be obtained.

The flame-retardant resin film made of such a thermoplastic resin composition is an intermediate material for producing the fiber-reinforced resin composite sheet in the present embodiment. A plurality of reinforcing fibers opened from a reinforcing fiber bundle are laminated in a state of being oriented in the same direction on one or both surfaces of a flame-retardant resin film, and heat, cool, and / or pressurize the fibers. The fiber reinforced resin composite sheet in this embodiment is obtained. From the viewpoint of obtaining more excellent flame-retardant properties, it is preferable that the plurality of reinforcing fibers are laminated on both surfaces of the flame-retardant resin film.

[Reinforcing fiber]
The reinforcing fibers are laminated on a flame-retardant resin film made of the above-mentioned thermoplastic resin composition in a state in which a plurality of reinforcing fibers opened from the reinforcing fiber bundles are oriented in the same direction. As used herein, the "state in which a plurality of reinforcing fibers are oriented in the same direction" means a state in which each reinforcing fiber extends in a substantially parallel direction with respect to the plurality of reinforcing fibers.

By laminating a plurality of reinforcing fibers on the flame-retardant resin film (specifically, on the surface of the flame-retardant resin film) in such a state, the fiber-reinforced resin composite sheet in the present embodiment is very stable. Has excellent flame retardancy. Specifically, not only the resin film itself has flame-retardant properties, but also a plurality of non-flammable reinforcing fibers (preferably carbon fibers) are exposed without being completely impregnated on the flame-retardant resin film. By being laminated in this state, the spread of the flame can be suppressed as compared with the sheet in which the reinforcing fibers are completely impregnated in the molten resin.

The material of the reinforcing fiber is not particularly limited, but is known as a reinforcing fiber constituting a fiber-reinforced resin composite sheet, and when the sheet is formed, the sheet satisfies the conditions of combustibility classification described in detail later. May be appropriately selected according to the intended use. As a specific example, various fibers such as carbon fiber, aramid fiber, glass fiber, boron fiber, alumina fiber, silicon nitride fiber, and basalt fiber can be used. Of these, carbon fibers, aramid fibers, glass fibers, boron fibers, alumina fibers, and silicon nitride fibers are preferable from the viewpoint of specific strength and specific elasticity. Further, carbon fiber is more preferable because the strength and corrosion resistance of the molded product using the fiber-reinforced resin composite sheet in the present embodiment can be improved. As the carbon fiber, it is preferable to use a PAN (polyacrylonitrile) -based carbon fiber having particularly high strength. When carbon fiber is used as the reinforcing fiber, the surface treatment with metal may be applied. The reinforcing fibers opened from these reinforcing fiber bundles can be used alone or in combination of two or more as long as they are oriented in the same direction.

In the fiber-reinforced resin composite sheet of the present embodiment, the volume content Vf of the reinforcing fibers with respect to the fiber-reinforced resin composite sheet is 30% or more and 65% or less. By setting the volume content Vf of the reinforcing fibers to 30% or more, the fiber-reinforced resin composite sheet is sufficiently reinforced by the reinforcing fibers, and therefore has excellent strength, particularly tensile strength. On the other hand, by setting the volume content Vf of the reinforcing fibers to 65% or less, it is possible to maintain good molding processability of the fiber-reinforced resin composite sheet made of the thermoplastic resin. Further, the fiber reinforcement is performed by adjusting the volume content Vf of the reinforcing fiber within the range of 30% or more and 65% or less while considering the type of the resin selected and the type and amount of the flame retardant added optionally. The resin composite sheet can meet the conditions of the flammability classification described in detail later.

The volume content Vf of the reinforcing fiber is preferably 35% or more, more preferably 40% or more, and further preferably 44% or more. The volume content Vf of the reinforcing fiber is preferably 60% or less, more preferably 55% or less, still more preferably 53% or less. The volume content Vf of the reinforcing fibers in the fiber-reinforced resin composite sheet is not only the type and thickness of the reinforcing fibers, the fiber width in which the reinforcing fibers are oriented, the thickness of the flame-retardant resin film, etc., but also the fiber-reinforced resin composite. It can be adjusted within the above range by appropriately controlling the temperature and pressure applied during the production of the sheet. The volume content Vf of the reinforcing fiber can be measured by a combustion method, a nitric acid decomposition method, a sulfuric acid decomposition method, or the like, but the volume content Vf of the reinforcing fiber in the present specification is measured by the same combustion method as in the examples. Value.

Further, the thickness of the fiber reinforced resin composite sheet in the present embodiment is 20 μm or more and 100 μm or less. The thickness of the fiber-reinforced resin composite sheet is preferably 25 μm or more, more preferably 30 μm or more, still more preferably 35 μm or more, still more preferably 40 μm or more. The thickness of the fiber-reinforced resin composite sheet is preferably 90 μm or less, more preferably 80 μm or less, still more preferably 70 μm or less, still more preferably 60 μm or less, 55 μm or less, or 50 μm or less.

Specifically, by reducing the thickness of the fiber-reinforced resin composite sheet as much as possible within the above range, the flame-retardant resin film and the reinforcing fiber are mostly fused and laminated, so that the reinforcing fiber is formed. You will be able to fully demonstrate the strength you have. In addition, when stress is applied, delamination of the laminate made of the fiber-reinforced composite sheet (fiber-reinforced resin composite material described later) is unlikely to occur, and the fatigue characteristics are also excellent. Further, the molding processability when the fiber reinforced resin composite sheet is used can be made more excellent. The thickness of the fiber-reinforced resin composite sheet is also affected by the thickness of the flame-retardant resin film, but it can be kept within the above range by appropriately controlling the temperature and pressure applied during the production of the fiber-reinforced resin composite sheet. can.

The fiber-reinforced resin composite sheet in this embodiment has a flammability classification of 5VA or 5V-B determined in the UL94-5V combustion test conforming to the ASTM D5048 standard. The UL94-5V combustion test conforming to the ASTM D5804 standard will be described in detail in Examples described later. Preferably, the flammability classification determined in the UL94-5V combustion test conforming to the ASTM D5048 standard is 5VA. As described above, the flammability of the fiber-reinforced resin composite sheet is 30% or more and 65% or less of the selected resin type, the type and amount of the flame retardant added optionally, and the volume content Vf of the reinforcing fiber. The condition of the combustibility classification can be satisfied by the adjustment ratio within the range of.

As described above, the fiber-reinforced resin composite sheet in the present embodiment not only has excellent flame-retardant and high heat-resistant physical properties, but is also excellent due to the volume content Vf of the reinforcing fiber occupying a sufficient value. It has a reinforcing effect, fatigue resistance, and excellent molding processability due to the relatively thin thickness of the fiber reinforced resin composite sheet. That is, the fiber-reinforced resin composite sheet in the present embodiment is a resin molded product such as a housing or part of an electric device such as a smartphone, a tablet, a notebook computer, or an electronic device, which may generate heat, ignite, or burn from the inside of the device. Etc. are preferably used as a material for producing the above. Furthermore, according to the fiber-reinforced resin composite sheet in the present embodiment, a plurality of fiber-reinforced resin composite sheets can be laminated to form various shapes at high density while reducing voids as much as possible, so that excellent strength can be obtained. It is possible to manufacture a fiber-reinforced resin composite material and a resin molded product.

An example of the method for manufacturing the fiber-reinforced resin composite sheet in the present embodiment will be described with reference to FIG. In FIG. 1, each reference numeral is a fiber reinforced resin composite sheet manufacturing apparatus 1, a heating roller 2, a cooling roller 3, an endless belt 4, a pull-out roller 5, a bobbin 6, a fiber reinforced resin composite sheet S, a flame-retardant resin film R0, and reinforced. It represents a fiber bundle F0 and a reinforcing fiber (reinforcing fiber opened (from the reinforcing fiber bundle) F).

The fiber-reinforced resin composite sheet S can be continuously manufactured by using, for example, the fiber-reinforced resin composite sheet manufacturing apparatus 1 shown in FIG. The fiber-reinforced resin composite sheet manufacturing apparatus 1 is an apparatus for continuously producing a fiber-reinforced resin composite sheet S from a flame-retardant resin film R0 composed of a reinforcing fiber bundle F0 and a thermoplastic resin composition.

Specifically, the fiber-reinforced resin composite sheet manufacturing apparatus 1 includes a plurality of pairs of heating rollers 2 arranged vertically (two pairs in FIG. 1) and a plurality of pairs arranged vertically below the heating rollers 2 (two pairs in FIG. 1). ), A pair of endless belts 4 hung between the heating roller 2 and the cooling roller 3, a pair of pull-out rollers 5 located below the endless belt 4, and under the pull-out roller 5. It is provided with a winding bobbin 6 arranged on the side.

Although not shown, a fiber opening mechanism for opening the reinforcing fiber bundle F0 and spreading it in a band shape is provided in the vicinity of the heating roller 2 on the uppermost stage. By continuously opening the reinforcing fiber bundle F0, this fiber opening mechanism can form a large number of continuous reinforcing fibers F while spreading them so as to be oriented in the same direction and extend. The fiber opening mechanism may be any mechanism capable of such processing, such as a mechanism for striking and expanding the reinforcing fiber bundle F0, a mechanism for blowing and expanding the reinforcing fiber bundle F0, and a mechanism for applying ultrasonic waves to the reinforcing fiber bundle F0. Various mechanisms such as a mechanism for spreading can be used.

In the example of FIG. 1, the fiber opening mechanism includes a mechanism for supplying the reinforcing fiber F after opening the fiber to one surface of the flame-retardant resin film R0 and a mechanism for supplying the reinforcing fiber F after opening the fiber to the other surface of the flame-retardant resin film R0. It has a mechanism for supplying the reinforcing fiber F of the above. The former mechanism is provided so as to introduce the reinforcing fiber F between one surface of the flame-retardant resin film R0 and the heating roller 2 in contact with the surface, and the latter mechanism is the flame-retardant resin film R0. The reinforcing fiber F is provided between the other surface and the heating roller 2 in contact with the surface. However, the fiber opening mechanism may supply the reinforcing fiber F only to one surface of the flame-retardant resin film R0.

The heating roller 2 is a high-temperature roller heated by an electric heater, a heating medium, or the like (for example, a heating fluid). The two pairs of heating rollers 2 heat the reinforcing fibers F while sandwiching the flame-retardant resin film R0 and the reinforcing fibers F introduced on both sides thereof from both sides via the endless belt 4, thereby heating the reinforcing fibers F with the flame-retardant resin film R0. It is continuously laminated on. The reinforcing fibers F are laminated on the flame-retardant resin film R0 in a state of being oriented in the same direction (a state of being aligned in the vertical direction of FIG. 1).

The cooling roller 3 is a low-temperature roller cooled by a cooling medium or the like (for example, a cooling fluid). The cooling roller 3 fixes the reinforcing fibers F to the flame-retardant resin film R0 by cooling the flame-retardant resin film R0 in which the reinforcing fibers F are laminated while sandwiching the flame-retardant resin film R0 from both sides via the endless belt 4. As a result, the fiber-reinforced resin composite sheet S in which the flame-retardant resin film R0 (resin matrix) and the reinforcing fibers F are integrated is formed.

The pull-out roller 5 is a roller that pulls out the molded fiber-reinforced resin composite sheet S downward while applying tension to it.

The bobbin 6 for winding is a core material for winding the fiber reinforced resin composite sheet S. The bobbin 6 is rotationally driven by a drive source such as a motor, and the fiber-reinforced resin composite sheet S drawn out by the drawing roller 5 is sequentially wound up to form a roll-shaped fiber-reinforced resin composite sheet S.

The fiber-reinforced resin composite sheet S can also be produced by a method in which the flame-retardant resin film R0 and the opened reinforcing fibers are flowed together in the same direction and wound without using the endless belt 4 shown in FIG. Is possible.

When the reinforcing fibers are laminated on one surface of the flame-retardant resin film R0 with the opened reinforcing fibers oriented in the same direction, the reinforcing fibers F shown in FIG. 1 are not sent from both sides. By feeding from one side, a fiber-reinforced resin composite sheet S in which reinforcing fibers F are laminated on one surface of a flame-retardant resin film can be obtained.

<Fiber reinforced plastic composite material>
The fiber-reinforced resin composite material in the present embodiment is a fiber-reinforced composite material in which a plurality of fiber-reinforced resin composite sheets in the above-described embodiment are laminated in the thickness direction.

Here, in the entire specification, the "lamination" used in "the fiber reinforced resin composite sheet (or its chop material) is laminated" means the physical properties of the fiber reinforced resin composite sheet (or its chop material). Depending on the value, shape, type of processing performed for lamination and its conditions, etc., "lamination after fixing at least partly", "lamination after bonding at least partly", "at least partly bonding" It also includes the meanings of "lamination after fusion in a part", "lamination after adhesion in at least a part", and "lamination after crimping in at least a part". More specifically, at the time of "lamination", heating, cooling and / or pressure treatment may be performed as necessary.

The fiber-reinforced resin composite sheet to be laminated may be laminated by being shredded or the like as necessary according to the desired shape of the fiber-reinforced resin composite material. The number of laminated fiber-reinforced resin composite sheets is also not particularly limited, and may be appropriately set according to the desired size of the fiber-reinforced resin composite material and the like. The fiber-reinforced resin composite sheet may be laminated in any state with respect to the fiber direction of the reinforcing fiber, but preferably, the fiber directions of the reinforcing fibers of the plurality of fiber-reinforced resin composite sheets differ in two-dimensional directions. It is laminated in a state of having.

For example, a plurality of fiber-reinforced resin composite sheets have an angle difference of approximately 45 ° in each of the fiber directions of the reinforcing fibers, in other words, 0 °, 45 °, −45 °, and 90 in the two-dimensional plane. Two or more sheets, preferably 4 × n sheets (n is an integer of 1 or more) are laminated in the thickness direction so as to have a four-axis direction of ° (hereinafter, also referred to as “four-axis direction with an angle difference of 45 °”). Examples of fiber-reinforced composite materials are available. By laminating the fiber-reinforced resin composite sheet in this way, the tensile strength and the bending strength along each fiber direction can be improved, so that the overall strength of the fiber-reinforced resin composite material is effectively improved. Can be made to.

Alternatively, as another fiber-reinforced resin composite material in the present embodiment, the fiber-reinforced resin composite sheet in the above-described embodiment may be laminated in the shape of a plurality of chops in the thickness direction.

A plurality of chop materials can be produced, for example, by shredding the fiber-reinforced resin composite sheet S shown in FIG. 1 in the above-described embodiment in the longitudinal direction and the width direction.

As a specific example, a chop material can be produced by the following procedure. The procedure will be described with reference to FIG. In FIG. 2, each reference numeral represents a fiber reinforced resin composite sheet S, a notch X, a notch Y, a section I, a section II, and a chop material C. First, as shown in FIG. 2, a notch X extending in the longitudinal direction is formed. That is, while feeding the fiber-reinforced resin composite sheet S in the longitudinal direction, a large number of cuts X continuous in the longitudinal direction are formed in the section I in the middle of the feeding path. The cut X can be formed by using, for example, a shredding device including a large number of blades arranged at equal intervals in the width direction of the fiber reinforced resin composite sheet S.

Next, in the subsequent section II, a continuous notch Y is formed from one end to the other end of the fiber reinforced resin composite sheet S in the width direction. The notch Y can be formed by using, for example, a rotary cutter or the like. The notch Y is formed each time the fiber reinforced resin composite sheet S is fed out by a fixed distance in the longitudinal direction. As a result, a large number of rectangular chop materials C having a short side having a length corresponding to the pitch of the cut X and a long side having a length corresponding to the pitch of the cut Y are cut out.

As described above, the fiber-reinforced resin composite sheet S is a sheet in which a large number of reinforcing fibers F are laminated in the same direction in the longitudinal direction thereof. Therefore, each chop material C cut out from the fiber-reinforced resin composite sheet S is also laminated in a state in which a large number of reinforcing fibers F are oriented in the same direction in the longitudinal direction (long side direction). That is, the chop material C contains a flame-retardant resin film R0 and a large number of reinforcing fibers F laminated on the flame-retardant resin film R0 in the same direction.

The larger the size of the chop material C, the higher the strength of the fiber-reinforced resin composite material or the resin molded product can be produced, but the shapeability thereof becomes lower. On the other hand, the smaller the size of the chop material C, the better the shapeability, and it is possible to manufacture a fiber-reinforced resin composite material or a resin molded product having a high degree of freedom, but the strength of the manufactured product decreases. .. In consideration of the balance between the shapeability and the mechanical properties depending on the size of the chop material C, the size of the chop material C is adjusted and the balance is appropriately controlled to impart properties suitable for the intended use of the molded product. can do.

The length of the short side of the chop material C is preferably 2 mm or more, more preferably 3 mm or more, further preferably 4 mm or more, still more preferably 4.5 mm or more, and preferably 50 mm or less, more preferably 40 mm. Hereinafter, it is more preferably 30 mm or less, or even more preferably 20 mm or less, 15 mm or less, or 10 mm or less. The length of the long side of the chop material C is preferably 2 mm or more, more preferably 4 mm or more, further preferably 6 mm or more, or even more preferably 8 mm or more or 10 mm or more, and preferably 80 mm or less. It is preferably 70 mm or less, more preferably 60 mm or less, or even more preferably 50 mm or less or 45 mm or less.

The thickness of the chop material C is the same as the thickness of the fiber-reinforced resin composite sheet in the above-described embodiment, and is 20 μm or more and 100 μm or less. The preferable thickness is also the same as the thickness of the fiber reinforced resin composite sheet in the above-described embodiment. That is, similarly to the fiber-reinforced resin composite sheet in the above-described embodiment, a plurality of sheets can be laminated in a small size as the chop material C while reducing the voids as much as possible due to its thinness. Therefore, it is possible to manufacture a fiber-reinforced resin composite material having a significantly higher density and remarkably excellent strength and low water absorption, and a resin molded product using the same. Further, by forming the chop material C into a shape, the shapeability is improved, and a resin molded product having a complicated shape can be manufactured.

In the fiber-reinforced composite material of the present embodiment, such a plurality of chop materials C may be laminated in any state of the fiber directions of the reinforcing fibers, but the fiber directions of the reinforcing fibers of the plurality of chop materials C. However, it is preferable that the fibers are laminated in a two-dimensionally random state (pseudo-isotropic).

An example of such a method for producing a fiber-reinforced composite material will be described with reference to FIG. In FIG. 3, each reference numeral represents a belt conveyor 7, a release film 8, a heating roller 9, a bobbin 10 for a laminated chopped sheet, a chop material C, a section XI, a section XII, a section XIII, and a laminated chopped sheet CS. There is. First, as shown in FIG. 3, while rotating the belt conveyor 7 which is arranged substantially horizontally and is rotating, a large number of chop materials C are arranged while being dispersed on the upper surface thereof. For the distributed arrangement of the chop material C, for example, a drop device that drops the chop material C while vibrating from above the belt conveyor 7 can be used. Then, by repeating the drop operation of the chop material C using such a drop device, the density and the number of laminated chop materials C on the upper surface of the belt conveyor 7 are increased. That is, in a plurality of sections XI, sections XII, sections XIII, ... In the rotation direction of the belt conveyor 7, the chop material C is contained in each chop material C by repeatedly dropping the chop material C using the drop device. A large number of reinforcing fibers F are placed on the belt conveyor 7 so that the fiber directions (in other words, the longitudinal direction of the chop material C) vary in various directions on the horizontal plane and a plurality of chop materials C are stacked in the thickness direction. Chop material C is laminated.

Then, from the terminal side on which a large number of chop materials C are laminated, the chop material C laminated on the upper surface of the belt conveyor 7 is pressurized and heated by using a heating roller 9 or a heat-resistant endless belt via a release film 8. It is processed and a large number of chop materials C are integrated. That is, the laminated chop materials C are bonded to each other by pressurization and heat treatment using the heating roller 9. As described above, the dispersion and lamination of a large number of chop materials C on the upper surface of the belt conveyor 7 and the pressurization and heat treatment using the heating roller 9 are continuously performed. After that, as a laminated chopped sheet CS in which a plurality of chopped materials C are integrally laminated with each other, a scroll-like continuous molding is performed using a bobbin 10 for a laminated chopped sheet or the like. A partial cross section of the continuously molded scroll-shaped laminated chopped sheet CS is shown in FIG. In FIG. 4, each reference numeral represents a thickness t of the chopped material C, the laminated chopped sheet (fiber reinforced composite material) CS, and the laminated chopped sheet CS. The thickness t of the laminated chopped sheet CS, that is, the total thickness of the chopped materials C in which a plurality of sheets or more are laminated can be appropriately set.

Alternatively, as another example of the method for producing a fiber-reinforced composite material, a large number of chopped materials C may be laminated on a carrier sheet made of a thermoplastic resin composition when producing a laminated chopped sheet.

Specifically, while feeding the carrier sheet in the longitudinal direction as in the belt conveyor 7 shown in FIG. 3, a large number of chop materials C are arranged while being dispersed on the upper surface of the carrier sheet. For the dispersed arrangement of the chop material C, for example, a dropping device similar to the above can be used from above the carrier sheet. Then, the drop operation of the chop material C using such a drop device is repeated at a plurality of places in the feed direction of the carrier sheet in the same manner as described above to increase the density and the number of laminated chop materials C on the carrier sheet. May be good. That is, a large number of chops are placed on the carrier sheet so that the fiber directions of the reinforcing fibers F contained in each chop material C vary in various directions on the horizontal plane and a plurality of chop materials C are stacked in the thickness direction. Material C may be laminated.

After that, the carrier sheet and the chop material C on the carrier sheet are pressurized and heat-treated using a heating roller to integrate the carrier sheet and the chop material C with each other. That is, by pressurizing and heat-treating using the heating roller, the chop material C is supported on the carrier sheet in a laminated state, and the laminated chop materials C are bonded to each other. By such a method, a laminated chopped sheet CS in which a plurality of chopping materials C are laminated on the upper surface of the carrier sheet can be formed.

The material of the carrier sheet is basically the same thermoplastic resin composition as the thermoplastic resin composition of the chop material C, a resin composition containing another thermoplastic resin having flame-retardant properties, or flame-retardant. A thermoplastic resin composition that does not have the above can be used. These thermoplastic resin compositions may consist of the thermoplastic resin alone without any additives.

Although the case where the chopped material C is laminated only on the upper surface of the carrier sheet to produce the laminated chopped sheet CS has been described, it is naturally possible to laminate the chop material C on both sides of the carrier sheet. In this case, it is preferable to perform the work of laminating the chop material C on the carrier sheet (that is, the work of arranging the chop material C in multiple random manners and heating and pressurizing the chop material C) in order on the upper surface and the lower surface of the carrier sheet. .. That is, after laminating the chop material C on the upper surface of the carrier sheet, the carrier sheet is turned over so that the lower surface of the carrier sheet is on top, and the operation of laminating the chop material C in that state is repeated in the same manner. As a result, a laminated chopped sheet in which the chopping material C is laminated on both sides of the carrier sheet can be produced.

<Resin molded product>
The resin molded product in this embodiment includes the fiber reinforced resin composite material in the above-described embodiment.

The resin molded product may be any molded product having an arbitrary shape that can be manufactured by using the fiber-reinforced resin composite material in the above-described embodiment by any molding method known to those skilled in the art. Examples thereof include molded products such as housings and parts used in electric devices such as smartphones, tablets, notebook computers, video cameras, mobile devices, and other household electric devices, or electronic devices.

The method for producing the resin molded product in this embodiment is not particularly limited. To give an example, first, a plurality of laminated chopped sheet CS described in the above-described embodiment, which are plate-shaped cut out to a predetermined size, are prepared, and these are stacked in the thickness direction in a mold such as a heat press machine. Place in. After that, a resin molded product can be manufactured by performing a heating and / or pressure treatment and, if necessary, a cooling treatment on a plurality of stacked laminated chopped sheet CS.

According to the manufacturing method as described above, since the flame-retardant resin film R0 made of a highly heat-resistant thermoplastic resin composition is used, the physical properties of the tensile strength and bending strength of the resin molded product even under high temperature conditions. It is possible to obtain a resin molded product whose value is unlikely to decrease. Further, since the resin molded product is molded using the laminated chopped sheet CS containing a sufficient amount of the reinforcing fiber F so that the volume content Vf of the reinforcing fiber is 30% or more and 65% or less, the reinforcing fiber F is used. An excellent reinforcing effect can be obtained, and the strength of the resin molded product can be increased. Furthermore, the laminated chopped sheet CS, which is laminated in a state where the fiber directions of the reinforcing fibers F of the plurality of chop materials C are two-dimensionally random (pseudo isotropic), is when the laminated chopped sheet CS is pressed. The possibility that the reinforcing fiber F is shredded can be reduced, and the flow of the resin during press working can be promoted to increase the degree of freedom in the shape of the resin molded product. As a result, resin molded products having various shapes can be molded without any trouble while exhibiting the reinforcing effect of the reinforcing fibers F isotropically.

The outline of the present invention has been described above, but the fiber-reinforced resin composite sheet, the fiber-reinforced resin composite material, and the resin molded product provided with the same are summarized below.

The fiber reinforced resin composite sheet having such a structure has excellent flame retardancy, good molding processability, and sufficient tensile strength under high temperature conditions.

It is preferable that the plurality of reinforcing fibers are laminated on one or both surfaces of the flame-retardant resin film.

In the fiber reinforced resin composite sheet having such a structure, since a plurality of reinforcing fibers are laminated on one or both surfaces of the flame-retardant resin film, the prepreg in which the reinforcing fibers are completely impregnated in the molten resin. Has very good flame retardancy compared to.

It is more preferable that the plurality of reinforcing fibers are laminated on both surfaces of the flame-retardant resin film.

The fiber-reinforced resin composite sheet having such a structure surely has extremely excellent flame retardancy as compared with the prepreg in which the reinforcing fibers are completely impregnated in the molten resin.

It is more preferable that the thermoplastic resin composition contains a polycarbonate resin and one or more flame retardants selected from a halogen-based flame retardant, a phosphorus-based flame retardant, a silicone-based flame retardant, and an inorganic flame retardant.

The fiber reinforced resin composite sheet having such a structure surely has excellent flame retardancy.

It is particularly preferable that the thermoplastic resin composition contains one or more selected from polyphenylene sulfide resin, polyetheretherketone resin, polyetherketoneketone resin, polyetherimide resin, polyethersulfone resin and liquid crystal polymer resin.

The reinforcing fiber is more preferably carbon fiber.

The fiber reinforced resin composite sheet having such a structure can improve the strength and corrosion resistance of the molded product using the fiber reinforced resin composite sheet, and the nonflammable carbon fiber surely has extremely excellent flame retardancy.

The thickness of the flame-retardant resin film is more preferably 5 μm or more and 50 μm or less.

The fiber-reinforced resin composite sheet having such a structure can be made thin even in the sheet itself, and as a result, can have good molding processability.

The fiber-reinforced resin composite material according to the second aspect of the present invention is a fiber-reinforced composite material in which a plurality of fiber-reinforced resin composite sheets of the fiber-reinforced resin composite sheet according to the first aspect are laminated in the thickness direction.
The fiber-reinforced composite material is laminated in a state in which the fiber directions of the reinforcing fibers of the plurality of fiber-reinforced resin composite sheets have an angle difference in the two-dimensional direction.

The fiber-reinforced resin composite material having such a structure can effectively improve the strength of the fiber-reinforced resin composite material as a whole.

Alternatively, the fiber-reinforced resin composite material according to the second aspect of the present invention is a fiber-reinforced composite material in which the fiber-reinforced resin composite sheet according to the first aspect is laminated in the shape of a plurality of chops in the thickness direction. And
The chop material is formed so that the fiber-reinforced resin composite sheet exhibits a rectangular shape having a short side length of 2 mm or more and 50 mm or less and a long side length of 2 mm or more and 80 mm or less.
The fiber-reinforced composite material is laminated in a state in which the fiber directions of the reinforcing fibers of the plurality of chop materials are two-dimensionally random.

The fiber-reinforced resin composite material having such a structure can mold resin molded products of various shapes without any trouble while exerting the reinforcing effect of the reinforcing fibers isotropically.

The resin molded product according to the third aspect of the present invention includes the fiber reinforced resin composite material according to the second aspect.

A resin molded product having such a structure has excellent flame retardancy and sufficient tensile strength under high temperature conditions.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to any examples.

The fiber-reinforced resin composite sheet and the test piece of the fiber-reinforced resin composite material of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-5 were prepared as follows.

(Example 1-1)
In order to prepare a fiber-reinforced resin composite sheet, a flame-retardant resin film made of a thermoplastic resin composition was prepared. In Example 1-1, a flame-retardant resin film containing a polycarbonate resin and made of a thermoplastic resin composition to which a non-bromine-based and non-phosphorus-based flame retardant was added was used. The glass transition temperature Tg of this thermoplastic resin composition is 148 ° C. to 150 ° C. The thickness of the flame-retardant resin film is 20 μm.

This flame-retardant resin film and carbon fiber (manufactured by Toray Co., Ltd., "TORAYCA", grade: T-700 (PAN-based carbon fiber), fiber diameter: 7 μm, number of filaments: 12K, fineness: 800tex) are used as reinforcing fibers. Using the manufacturing apparatus shown in FIG. 1, the fiber-reinforced resin composite sheet according to the above-described embodiment was obtained while opening the carbon fiber bundle. At this time, the pressing force was 0.5 MPa, the roll temperature (the temperature of the heating roller 2 shown in FIG. 1) was 270 ° C., and the feed rate was 10 m / min. In the obtained fiber-reinforced resin composite sheet, the opened carbon fiber bundles are laminated on both sides of the flame-retardant resin film. The volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 53%, and the thickness of the fiber-reinforced resin composite sheet was 40 μm to 50 μm.

40 sheets of the obtained fiber-reinforced resin composite sheet were laminated so that the opened carbon fibers were oriented at an angle difference of 0 °. The laminated fiber-reinforced resin composite sheet was put into a mold and pressurized while heating at 300 ° C. and 2 MPa for 15 minutes, and then pressurized while cooling at room temperature and 3 MPa for 10 minutes. A 300 mm × 300 mm × 2 mm (thickness) fiber reinforced resin composite material is taken out from the mold, the fiber reinforced resin composite material is cut out, and a test piece of the 150 mm × 150 mm × 2 mm (thickness) fiber reinforced resin composite material is cut out. Obtained. The volume content Vf of the carbon fiber of the test piece was also 53%.

(Example 1-2)
In Example 1-2, instead of the thermoplastic resin composition containing the polycarbonate resin to which the flame-retardant agent of Example 1-1 was added, a polyphenylene sulfide (PPS) resin having flame-retardant properties (manufactured by Solvay, “Ryton ( A thermoplastic resin composition consisting only of the registered trademark) QC200N ”) was used. The glass transition temperature Tg of the thermoplastic resin composition made of polyphenylene sulfide (PPS) resin is 90 ° C. Pellets of polyphenylene sulfide (PPS) resin are set under conditions of a molding temperature of 280 ° C. using an extrusion molding machine equipped with a T-die, and a flame-retardant resin film made of polyphenylene sulfide (PPS) resin having a thickness of 25 μm. Was produced.

Using this flame-retardant resin film and the carbon fibers described in Example 1-1, a fiber-reinforced resin composite sheet was obtained while opening the carbon fiber bundles by the manufacturing apparatus shown in FIG. At this time, the pressing force was 0.5 MPa, the roll temperature (the temperature of the heating roller 2 shown in FIG. 1) was 280 ° C., the feed rate was 20 m / min, and the fiber reinforcement had the same shape as that of Example 1-1. A resin composite sheet was obtained. The volume content Vf of the carbon fiber with respect to the fiber-reinforced resin composite sheet was 44.7%, and the thickness of the fiber-reinforced resin composite sheet was 50 μm.

Using the obtained fiber-reinforced resin composite sheet, a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) was obtained by the same method as in Example 1-1 described above. The volume content Vf of the carbon fiber of the test piece was also 44.7%.

(Example 1-3)
When laminating the fiber-reinforced resin composite sheet of carbon fiber so that the volume content Vf of the carbon fiber with respect to the fiber-reinforced resin composite sheet is 35%, a film made of polyphenylene sulfide (PPS) resin having a thickness of 25 μm is further added. Except for the above, test pieces of a fiber-reinforced resin composite sheet having a thickness of 50 μm and a fiber-reinforced resin composite material having a thickness of 150 mm × 150 mm × 2 mm (thickness) were obtained by the same method as in Example 1-2 described above. ..

(Example 1-4)
Instead of the flame-retardant resin film made of polyphenylene sulfide (PPS) resin having a thickness of 25 μm produced in Example 1-2, polyetheretherketone (PEEK) having flame-retardant properties and having a thickness of 20 μm. ) A resin film (manufactured by Mitsubishi Chemical, "Superio UT (registered trademark) αKN-type") was used. The glass transition temperature Tg of the thermoplastic resin composition made of polyetheretherketone (PEEK) resin is 143 ° C to 147 ° C.

Using this flame-retardant resin film and the carbon fibers described in Example 1-1, a fiber-reinforced resin composite sheet was obtained while opening the carbon fiber bundles by the manufacturing apparatus shown in FIG. At this time, the pressing force was 0.5 MPa, the roll temperature (the temperature of the heating roller 2 shown in FIG. 1) was 360 ° C., the feed rate was 10 m / min, and the fiber reinforcement had the same shape as that of Example 1-1. A resin composite sheet was obtained. The volume content Vf of the carbon fiber with respect to the fiber-reinforced resin composite sheet was 53%, and the thickness of the fiber-reinforced resin composite sheet was 40 μm.

Using the obtained fiber-reinforced resin composite sheet, a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) was obtained by the same method as in Example 1-1 described above. The volume content Vf of the carbon fiber of the test piece was also 53%.

(Comparative Example 1-1)
As Comparative Example 1-1, a commercially available fiber-reinforced resin composite sheet of a polyamide 6 resin matrix (“TC910” manufactured by TCAC), which is produced by impregnating a carbon fiber bundle into a molten resin as it is without opening the fibers. Was used. The glass transition temperature Tg of the polyamide 6 resin matrix is about 50 ° C. (reference value). The volume content Vf of the carbon fiber with respect to the fiber-reinforced resin composite sheet was 48%, and the thickness of the fiber-reinforced resin composite sheet was 180 μm.

14 fiber-reinforced resin composite sheets were laminated so that the carbon fiber bundles had an angle difference of approximately 0 °. Then, a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) was obtained by the same method as in Example 1-1 described above. The volume content Vf of the carbon fiber of the test piece was also 48%.

(Comparative Example 1-2)
In Comparative Example 1-2, the carbon fibers laminated on both sides of the flame-retardant resin film containing the polycarbonate resin to which the flame-retardant was added so that the volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 25%. A fiber-reinforced resin composite sheet having a thickness of 30 μm was obtained by the same method as in Example 1-1 described above except that the amount was reduced.

74 sheets of the obtained fiber-reinforced resin composite sheet were laminated so that the opened carbon fibers were oriented at an angle difference of 0 °. Then, a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) was obtained by the same method as in Example 1-1 described above. The volume content Vf of the carbon fiber of the test piece was also 25%.

(Comparative Example 1-3)
In Comparative Example 1-3, the carbon fibers laminated on both sides of the flame-retardant resin film containing the polycarbonate resin to which the flame-retardant was added so that the volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 70%. A fiber-reinforced resin composite sheet having a thickness of 70 μm was obtained by the same method as in Example 1-1 described above except that the amount was increased.

Using the obtained fiber-reinforced resin composite sheet, an attempt was made to prepare a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) by the same method as in Example 1-1 described above. The test piece could not be molded due to poor impregnation with the resin.

(Comparative Example 1-4)
In Comparative Example 1-4, the amount of carbon fibers laminated on both sides of the flame-retardant resin film made of polyphenylene sulfide (PPS) resin so that the volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet is 25%. A fiber-reinforced resin composite sheet having a thickness of 35 μm was obtained by the same method as in Example 1-2 described above, except that the amount was reduced.

64 sheets of the obtained fiber-reinforced resin composite sheet were laminated so that the opened carbon fibers were oriented at an angle difference of 0 °. Then, a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) was obtained by the same method as in Example 1-2 described above. The volume content Vf of the carbon fiber of the test piece was also 25%.

(Comparative Example 1-5)
In Comparative Example 1-5, the amount of carbon fibers laminated on both sides of the flame-retardant resin film made of polyphenylene sulfide (PPS) resin so that the volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet is 70%. A fiber-reinforced resin composite sheet having a thickness of 85 μm was obtained by the same method as in Example 1-2 described above, except that the amount was increased.

Using the obtained fiber-reinforced resin composite sheet, an attempt was made to prepare a test piece of a fiber-reinforced resin composite material having a size of 150 mm × 150 mm × 2 mm (thickness) by the same method as in Example 1-2 described above. The test piece could not be molded due to poor impregnation with the resin.

The volume content Vf of the reinforcing fiber with respect to the reinforced resin composite sheet and the fiber reinforced resin composite material was measured by the combustion method. The glass transition temperature Tg of each thermoplastic resin composition or the thermoplastic resin itself is a temperature measured by a differential scanning calorimeter (DSC).

<Evaluation of flame retardancy of thermoplastic resin film or resin matrix>
The resin films produced in Examples 1-1 to 1-4 and Comparative Examples 1-2 to 1-5 and the polyamide 6 resin matrix used in Comparative Example 1-1 conform to the ASTM D4804 standard. The flammability was determined by the UL94 VTM combustion test. Specifically, a test piece (dimensions: 200 ± 5 mm × 50 ± 1 mm × tmm) is wound in a cylindrical shape, mounted vertically on a clamp, and indirect flame for 3 seconds with a 20 mm flame is performed twice. The determination of "-0", "VTM-1", "VTM-2" or "Not" was performed. The t = 20 to 25 μm was set. Specific criteria are shown in Table 1 below.

<Evaluation of flame retardancy of fiber reinforced resin composite sheet>
UL94- conforming to the ASTM D5048 standard for the test pieces of the fiber-reinforced resin composite sheet produced in Examples 1-1 to 1-4 and Comparative Example 1-1, Comparative Example 1-2 and Comparative Example 1-4. Its flammability was determined in a 5V combustion test. Specifically, a strip-shaped test piece (dimensions: 125 ± 5 mm × 13 ± 0.5 × tmm) was vertically attached to the clamp, and a 5-second indirect flame with a 125 mm flame was performed 5 times. Further, the flat plate test piece (dimensions: 150 ± 5 mm × 150 ± 5 × tmm) was held horizontally, and a 5-second indirect flame of 125 mm flame was performed 5 times from below. Based on these combustion behaviors, "5V-B", "5VA" or "Not" was determined. In addition, t = 2 mm was set. Specific criteria are shown in Table 2 below. In Comparative Examples 1-3 and 1-5, the test piece of the fiber-reinforced resin composite sheet could not be tested because the impregnation property between the fiber and the resin was poor.

<Evaluation of tensile strength (MPa) of test piece of fiber reinforced resin composite material>
Tensile strength of the test pieces of the fiber-reinforced resin composite material of Examples 1-1 to 1-4, Comparative Example 1-1, Comparative Example 1-2 and Comparative Example 1-4 according to JIS K 7165: 2008. Was measured. In Comparative Examples 1-3 and 1-5, as described above, the test piece of the fiber reinforced resin composite material could not be molded, so that the test could not be performed.

Table 3 below shows the characteristics and evaluation results of the thermoplastic resin film or resin matrix and the fiber-reinforced resin composite sheet in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-5. And are summarized in Table 4.

As is clear from the results in Table 3 above, the resin films of Examples 1-1 to 1-4 and the fiber-reinforced resin composite sheet thereof are the polyamide 6 resin matrix of Comparative Example 1-1 and the fiber-reinforced resin composite thereof. It had excellent flame retardancy as compared with the sheet.

Further, the fiber-reinforced resin composite sheets of Examples 1-1 to 1-4 are the same as the fiber-reinforced resin composite sheets of Comparative Example 1-1 produced by impregnating the resin matrix with the carbon fiber bundles without opening the fibers. In comparison, the thickness could be significantly reduced. In addition, the test pieces of the fiber-reinforced resin composite material of Examples 1-2 and 1-3 have a volume content of the reinforcing fibers as compared with the test pieces of the fiber-reinforced resin composite material of Comparative Example 1-1. Despite the small value of Vf, it had high tensile strength, contrary to the normally expected result. This is because the fiber-reinforced resin composite sheets of Examples 1-1 to 1-4 are composed of many layers of thin fiber-reinforced resin composite sheets, and therefore have good dispersibility between the reinforcing fibers and the resin. Therefore, it is presumed that, as compared with the laminated board in Comparative Example 1-1 composed of a thick layer, delamination is less likely to occur and the original strength of the fiber is exhibited. As described above, the fiber-reinforced resin composite sheets of Examples 1-1 to 1-4 are excellent in molding processability as an intermediate material, and also have the tensile strength of the fiber-reinforced resin composite material produced from the sheets. It was excellent.

Further, as can be seen from the results of Comparative Examples 1-2 and 1-4 in Table 4 above, when the volume content Vf of the reinforcing fibers is reduced to 25%, the tensile strength of the fiber reinforced resin composite material becomes remarkable. It has dropped. Further, as can be seen from the results of Comparative Examples 1-3 and 1-5 in Table 4 above, when the volume content Vf of the reinforcing fibers is increased to 70%, the fibers in the obtained fiber-reinforced resin composite sheet are used. The fiber-reinforced resin composite material could not be molded because the impregnation property with the resin was deteriorated, and as a result, the molding processability was deteriorated. From these results, if the volume content Vf of the reinforcing fiber is not adjusted to a value within a specific range specified in the fiber reinforced resin composite sheet of the present embodiment, good molding processability and sufficient under high temperature conditions are sufficient. It can be seen that it is not possible to obtain a fiber-reinforced resin composite sheet that has both excellent tensile strength.

The glass transition temperature Tg of the resin film (thermoplastic resin composition or thermoplastic resin) used in Examples 1-1 to 1-4 is the glass of the polyamide 6 resin matrix used in Comparative Example 1-1. It is a value significantly higher than the transition temperature Tg. Therefore, the fiber-reinforced resin composite sheet of Examples 1-1 to 1-4 and the fiber-reinforced resin composite material produced from the fiber-reinforced resin composite sheet have heat resistance and have good strength even under high temperature conditions, for example, tensile strength ( Or it is assumed to have bending strength). Further, the thermoplastic resins (polyetherketone-ketone (PEKK) resin, polyetherimide (PEI) resin, polyethersulfone (PES)) of Reference Examples 1 to 4 having a high glass transition temperature Tg and high flammability shown in Table 5 below. ) Resin and liquid crystal polymer (LCP) resin) are also expected to exert the same effects as those of the present invention.

Furthermore, an additional experiment was conducted to evaluate the flame retardancy of the fiber reinforced resin composite sheet. Specifically, an additional experiment was conducted to investigate the relationship between the structure of the fiber-reinforced resin composite sheet and the flame-retardant properties of the sheet. First, test pieces of the fiber-reinforced resin composite sheet in Example 2-1 and Example 2-2 and Comparative Example 2-1 and Comparative Example 2-2 were prepared by the following methods.

(Example 2-1)
In Example 2-1 a fiber-reinforced resin composite sheet containing a polycarbonate resin to which a flame retardant was added was obtained by the same method as in Example 1-1 described above. The volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 53%, and the thickness of the fiber-reinforced resin composite sheet was 40 to 50 μm. Next, a test piece of a fiber-reinforced resin composite sheet having a size of 13 mm × 125 mm × 40 to 50 μm (thickness) was cut out from the obtained fiber-reinforced resin composite sheet.

The cross section of the test piece of the prepared fiber-reinforced resin composite sheet was observed using a laser microscope ("VK-X160", manufactured by Keyence Corporation). As shown in FIG. 5, in the cross-sectional view of the test piece of the fiber-reinforced resin composite sheet in Example 2-1, a plurality of carbon fibers are laminated on both sides of a flame-retardant resin film containing a polycarbonate resin to which a flame-retardant is added. In this state, specifically, a plurality of carbon fibers are impregnated from the surface of the film to the inside in about half of each carbon fiber.

(Example 2-2)
In Example 2-2, a fiber reinforced resin composite sheet containing a polyphenylene sulfide (PPS) resin was obtained by the same method as in Example 1-2 described above. The volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 44.7%, and the thickness of the fiber-reinforced resin composite sheet was 50 μm. Next, a test piece of a fiber-reinforced resin composite sheet having a size of 13 mm × 125 mm × 50 μm (thickness) was cut out from the obtained fiber-reinforced resin composite sheet.

The cross section of the test piece of the prepared fiber reinforced resin composite sheet was observed by the same method as in Example 2-1. As shown in FIG. 5, in the cross-sectional view of the test piece of the fiber-reinforced resin composite sheet in Example 2-2, a plurality of carbon fibers are laminated on both sides of a flame-retardant resin film made of polyphenylene sulfide (PPS) resin. In this state, specifically, a plurality of carbon fibers were impregnated from the surface of the film to the inside in about half of each carbon fiber.

(Comparative Example 2-1)
In Comparative Example 2-1 first, a fiber-reinforced resin composite sheet containing a polycarbonate resin to which a flame retardant was added was obtained by the same method as in Example 1-1 described above. Further, the sheet is sandwiched between iron plates heated to 300 ° C. and pressed by a press machine at 5 kgf × 60 seconds to obtain a fiber reinforced resin composite sheet containing the polycarbonate resin to which the flame retardant added in Comparative Example 2-1 is added. rice field. The volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 53%, and the thickness of the fiber-reinforced resin composite sheet was 38 μm. Next, a test piece of a fiber-reinforced resin composite sheet having a size of 13 mm × 125 mm × 38 μm (thickness) was cut out from the obtained fiber-reinforced resin composite sheet.

The cross section of the test piece of the prepared fiber reinforced resin composite sheet was observed by the same method as in Example 2-1. As shown in FIG. 5, the cross-sectional view of the test piece of the fiber-reinforced resin composite sheet in Comparative Example 2-1 shows that a plurality of carbon fibers are completely contained inside a flame-retardant resin film containing a polycarbonate resin to which a flame retardant is added. It was in a state of being impregnated.

(Comparative Example 2-2)
In Comparative Example 2-2, first, a fiber reinforced resin composite sheet containing a polyphenylene sulfide (PPS) resin was obtained by the same method as in Example 1-2 described above. Further, the sheet was sandwiched between iron plates heated to 330 ° C. and pressed at 5 kgf × 60 seconds using a press to obtain a fiber reinforced resin composite sheet containing the polyphenylene sulfide (PPS) resin in Comparative Example 2-2. .. The volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was 44.7%, and the thickness of the fiber-reinforced resin composite sheet was 42 μm. Next, a test piece of a fiber-reinforced resin composite sheet having a size of 13 mm × 125 mm × 42 μm (thickness) was cut out from the obtained fiber-reinforced resin composite sheet.

The cross section of the test piece of the prepared fiber reinforced resin composite sheet was observed by the same method as in Example 2-1. As shown in FIG. 5, in the cross-sectional view of the test piece of the fiber reinforced resin composite sheet in Comparative Example 2-2, a plurality of carbon fibers are completely impregnated in the flame-retardant resin film made of polyphenylene sulfide (PPS) resin. It was in a state of being.

<Additional flame retardancy test of fiber reinforced resin composite sheet>
The flame retardancy of the test pieces of the fiber-reinforced resin composite sheet produced in Example 2-1 and Example 2-2 and Comparative Example 2-1 and Comparative Example 2-2 was determined by a method different from the above-mentioned method. bottom. As a test method, first, a test piece of the produced fiber-reinforced resin composite sheet was hung with a clamp. Next, the flame of the prepared gas burner was adjusted to be blue. Then, the gas burner was moved so that the test piece of the fiber reinforced resin composite sheet suspended by the clamp was positioned at a place about 1 cm away from the tip of the flame of the gas burner. In this way, a flame was applied from the lower part of the test piece of the fiber reinforced resin composite sheet suspended by the clamp, and the state at the initial stage of ignition, specifically, 1 second after ignition was observed.

FIG. 6 is an image showing the result of a flame retardant additional test of a test piece of each fiber reinforced resin composite sheet. Specifically, FIG. 6 is an image of each fiber-reinforced resin composite sheet test piece 1 second after ignition. As can be seen from FIG. 6, the test pieces of Example 2-1 and Example 2-2 in which carbon fibers were impregnated from the surface of the film to the inside in approximately half of each carbon fiber were resin films. It was observed that the flame was less likely to spread as compared with the test pieces of Comparative Example 2-1 and Comparative Example 2-2 in which a plurality of carbon fibers were completely impregnated inside. This is because the test pieces of Example 2-1 and Example 2-2 are laminated on a flame-retardant resin film in an exposed state without being completely impregnated with a plurality of non-flammable carbon fibers. It is probable that the spread of the carbon fiber was suppressed. As described above, the fiber-reinforced resin composite sheet in the present embodiment has a structure in which not only the resin film has flame-retardant properties but also a plurality of reinforcing fibers are laminated on the flame-retardant resin film. Therefore, it is considered to have very excellent flame retardancy.

This application is based on Japanese Patent Application No. 2020-075392 filed on April 21, 2020, the contents of which are included in the present application.

In order to express the present invention, the present invention has been appropriately and sufficiently described through the embodiments and examples with reference to specific examples and the like, but those skilled in the art can modify and / or modify the above-described embodiments and examples. Or it should be recognized that improvements can be made easily. Therefore, unless the modified or improved form implemented by a person skilled in the art is at a level that deviates from the scope of rights of the claims stated in the claims, the modified form or the improved form is the scope of rights of the claims. It is interpreted as being comprehensively included in.

INDUSTRIAL APPLICABILITY The present invention can improve the flame retardancy, moldability and strength of a sheet under high temperature conditions in the technical field related to a fiber reinforced resin composite sheet, and is an industrial member such as a sports or leisure member, an automobile or an aircraft. , Can be widely used as a material for housings and parts of electrical equipment or electronic equipment.

Claims

A flame-retardant resin film made of a thermoplastic resin composition having a glass transition temperature Tg of 90 ° C. or higher, and a plurality of reinforcing fibers opened from a reinforcing fiber bundle are oriented in the same direction on the flame-retardant resin film. A fiber-reinforced resin composite sheet containing a plurality of laminated reinforcing fibers.
The flammability classification of the flame-retardant resin film determined in the UL94 VTM combustion test conforming to the ASTM D4804 standard is VTM-0.
The volume content Vf of the reinforcing fiber is 30% or more and 65% or less.
The thickness of the fiber reinforced resin composite sheet is 20 μm or more and 100 μm or less.
A fiber-reinforced resin composite sheet in which the flammability classification of the fiber-reinforced resin composite sheet determined in the UL94-5V combustion test conforming to the ASTM D5048 standard is 5VA or 5V-B.
The fiber-reinforced resin composite sheet according to claim 1, wherein the reinforcing fibers are laminated on both surfaces of the flame-retardant resin film.
The thermoplastic resin composition includes a polycarbonate resin and one or more flame retardants selected from a halogen-based flame retardant, a phosphorus-based flame retardant, a silicone-based flame retardant, and an inorganic flame retardant, according to claim 1 or 2. The fiber-reinforced resin composite sheet described in.
The thermoplastic resin composition comprises one or more selected from a polyphenylene sulfide resin, a polyether ether ketone resin, a polyether ketone ketone resin, a polyetherimide resin, a polyether sulfone resin, and a liquid crystal polymer resin. Alternatively, the fiber-reinforced resin composite sheet according to 2.
The fiber-reinforced resin composite sheet according to any one of claims 1 to 4, wherein the reinforcing fiber is a carbon fiber.
The fiber-reinforced resin composite sheet according to any one of claims 1 to 5, wherein the flame-retardant resin film has a thickness of 5 μm or more and 50 μm or less.
The fiber-reinforced resin composite sheet according to any one of claims 1 to 6 is a fiber-reinforced composite material in which a plurality of fiber-reinforced resin composite sheets are laminated in the thickness direction.
The fiber-reinforced composite material is a fiber-reinforced resin composite material in which a plurality of fiber-reinforced resin composite sheets are laminated in a state in which the fiber directions of the reinforcing fibers have an angle difference in a two-dimensional direction.
The fiber-reinforced resin composite sheet according to any one of claims 1 to 6 is a fiber-reinforced composite material laminated in the thickness direction in the shape of a plurality of chop materials.
The chop material is formed so that the fiber-reinforced resin composite sheet exhibits a rectangular shape having a short side length of 2 mm or more and 50 mm or less and a long side length of 2 mm or more and 80 mm or less.
The fiber-reinforced composite material is a fiber-reinforced resin composite material in which a plurality of chop materials are laminated in a state in which the fiber directions of the reinforcing fibers are two-dimensionally random.
A resin molded product comprising the fiber-reinforced resin composite material according to claim 7 or 8.