Fiber-reinforced resin composite material and molded article using same

Abstract

Provided is a fiber-reinforced resin composite material comprising a thermoplastic resin composition (X) and an inorganic fiber material (Y), the thermoplastic resin composition (X) comprising a thermoplastic resin and a phosphorus-based flame retardant, the phosphorus-based flame retardant comprising an intumescent flame retardant, and the inorganic fiber material (Y) having an elongation of 5% or less at a maximum load. According to the present invention, it is possible to provide a fiber-reinforced resin composite material having both high flame shielding properties and shock wave resistant strength.

Description

Technical Field

[0001] The present invention relates to a fiber-reinforced resin composite material and a molded product using the fiber-reinforced resin composite material. Background Art

[0002] In recent years, as part of environmental protection measures, research and development of electric vehicles and hybrid vehicles are being promoted, and high-energy-density battery development and lightweighting are being actively promoted to increase the cruising range. Such high-energy-density batteries have the potential to catch fire due to accidents. As a safety measure for passengers, the shell material needs to have high flame shielding properties. Therefore, in many cases, metal materials such as iron and refractory materials are used in combination.

[0003] However, metal materials have the disadvantage of being heavy, and when used in combination with refractory materials, processability and increased costs due to the increase in the number of parts become problems. Therefore, attempts have been made to make resins that can take into account both lightweight and flame shielding properties. Currently, in a society oriented towards sustainable development, the suppression of carbon dioxide and recyclability are gradually gaining attention. Thermosetting materials often have high flame retardancy and are very common as composite materials, but from the perspective of recyclability, thermoplastic resin raw materials are advantageous.

[0004] In addition, China has issued safety standards such as GB 38031-2020 "Safety Requirements for Power Batteries for Electric Vehicles", which stipulates that a warning must be issued 5 minutes before the battery's thermal runaway. It can be assumed that this can also be achieved through the shell material that shields the flame for more than 5 minutes after the battery catches fire.

[0005] To address these problems, for example, Patent Document 1 proposes a material in which a bromine-based flame retardant or an antimony oxide compound is added to a carbon fiber-reinforced polypropylene resin. However, the additives used here have a problem in terms of biopersistence.

[0006] In contrast, Patent Document 2 proposes a flame-retardant polyolefin composition containing a (poly)phosphate compound in a polyolefin resin as a technique for flame-retarding a polypropylene resin in consideration of biopersistence.

[0007] In addition, Patent Document 3 proposes a flame-retardant resin composition comprising long glass fibers and a phosphate compound contained in a polypropylene resin.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2014-62189

[0011] Patent Document 2: Japanese Patent Application Publication No. 2013-119575

[0012] Patent Document 3: Japanese Patent Application Publication No. 2011-88970 Summary of the invention

[0013] Problems to be solved by the invention

[0014] There are many deficiencies in the existing fiber-reinforced resin composite technology that can achieve both lightweight and flame shielding properties for high energy density batteries. Specifically, there are the following problems: the punchable sheet used to obtain the fiber-reinforced resin composite material cannot maintain fluidity during stamping, and sufficient strength and rigidity of the fiber-reinforced resin composite material cannot be obtained after stamping.

[0015] In particular, in the case of a high energy density battery, there is a possibility that a shock wave will be generated due to an explosion in the event of a runaway condition, and a strength capable of withstanding such a shock wave may be required.

[0016] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a fiber-reinforced resin composite material having both high flame shielding properties and strength to withstand shock waves.

[0017] Solutions to the problem

[0018] The present inventors have conducted intensive studies to solve the above problems and have found that a fiber-reinforced resin composite material comprising a thermoplastic resin composition containing a phosphorus-based flame retardant and a specific inorganic fiber material can solve the above problems. Based on these findings, the present invention has been completed.

[0019] That is, the present invention provides the following [1] to

[15] .

[0020] [1] A fiber-reinforced resin composite material comprising a thermoplastic resin composition (X) and an inorganic fiber material (Y),

[0021] The thermoplastic resin composition (X) comprises a thermoplastic resin and a phosphorus-based flame retardant,

[0022] The phosphorus-based flame retardant includes an intumescent flame retardant.

[0023] The inorganic fiber material (Y) has an elongation of 5% or less at the maximum load.

[0024] [2] The fiber-reinforced resin composite material according to [1] above, comprising at least one layer (A) and at least one layer (B) below:

[0025] a layer (A) in which the ratio of the weight of the thermoplastic resin composition (X) per unit area to the weight of the inorganic fiber material (Y) is relatively large, and

[0026] The layer (B) has a relatively small ratio of the weight of the thermoplastic resin composition (X) to the weight of the inorganic fiber material (Y) per unit area.

[0027] [3] The fiber-reinforced resin composite material according to [1] or [2] above, wherein:

[0028] The total weight ratio of the thermoplastic resin composition (X) to the inorganic fiber material (Y) is 70 / 30 to 30 / 70.

[0029] [4] The fiber-reinforced resin composite material according to any one of [1] to [3] above, wherein

[0030] The total weight ratio of the thermoplastic resin composition (X) to the inorganic fiber material (Y) is 60 / 40 to 30 / 70.

[0031] [5] The fiber-reinforced resin composite material according to any one of [2] to [4] above, wherein

[0032] The thickness ratio of the above-mentioned layer (A) to the layer (B) is 1 / 99 to 50 / 50.

[0033] [6] The fiber-reinforced resin composite material according to any one of [1] to [5] above, wherein

[0034] The above-mentioned thermoplastic resin composition (X) further contains a dispersant.

[0035] [7] The fiber-reinforced resin composite material according to [6] above, wherein

[0036] The above dispersant includes a copolymer of an α-olefin and an unsaturated carboxylic acid.

[0037] [8] The fiber-reinforced resin composite material according to [6] or [7] above, wherein:

[0038] The content of the dispersant is greater than 0 and less than 25 parts by mass based on 100 parts by mass of the phosphorus-based flame retardant.

[0039] [9] The fiber-reinforced resin composite material according to any one of [1] to [8] above, wherein

[0040] The inorganic fibers constituting the inorganic fiber material (Y) include at least one selected from the group consisting of glass fibers, ceramic fibers, metal fibers, and metal oxide fibers.

[0041]

[10] The fiber-reinforced resin composite material according to any one of [1] to [9] above, wherein

[0042] The inorganic fiber material (Y) includes an inorganic fiber fabric.

[0043]

[11] The fiber-reinforced resin composite material according to any one of [1] to

[10] above, wherein

[0044] The thermoplastic resin constituting the thermoplastic resin composition (X) includes a polypropylene-based resin, and the content of the polypropylene-based resin is 15 to 80% by mass based on the total weight.

[0045]

[12] The fiber-reinforced resin composite material according to any one of [1] to

[11] above, wherein

[0046] The content of the phosphorus-based flame retardant is 1 to 30% by mass based on the total weight.

[0047]

[13] A molded body obtained by press-molding the fiber-reinforced resin composite material according to any one of [1] to

[12] above.

[0048]

[14] A housing or a frame using the fiber-reinforced resin composite material described in any one of [1] to

[12] above.

[0049]

[15] A battery case using the fiber-reinforced resin composite material described in any one of [1] to

[12] above.

[0050] Effects of the Invention

[0051] According to the present invention, a fiber-reinforced resin composite material having both high flame shielding properties and strength to withstand shock waves can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a schematic diagram showing one embodiment of the fiber-reinforced resin composite material of the present invention.

[0053] Figure 2 It is a schematic diagram showing the method for producing the fiber-reinforced resin composite material of the present invention.

[0054] Figure 3 Schematic diagram showing a method for producing a fiber-reinforced resin composite material according to Example 1.

[0055] Figure 4 This is a schematic diagram showing a method for producing a fiber-reinforced resin composite material according to Example 2.

[0056] Explanation of symbols

[0057] 10Fiber reinforced resin composite materials

[0058] 11th floor (A)

[0059] 12th floor (B)

[0060] 20-layer stack

[0061] 21PP sheet (sheet formed from the thermoplastic resin composition (X))

[0062] 21'PP sheet

[0063] 21''PP sheet

[0064] 22 Glass fiber fabric mat (sheet formed of inorganic fiber material (Y))

[0065] 22' Fiberglass Fabric Mat DETAILED DESCRIPTION

[0066] Hereinafter, an embodiment of the present invention will be described in detail. However, the following description is an example of the embodiment of the present invention, and the present invention is not limited to these contents at all.

[0067] [Fiber-reinforced resin composite materials]

[0068] The present invention relates to a fiber-reinforced resin composite material comprising a thermoplastic resin composition (X) and an inorganic fiber material (Y). The thermoplastic resin composition (X) in the composite material of the present invention comprises a thermoplastic resin and an intumescent flame retardant as a phosphorus flame retardant. In addition, the inorganic fiber material (Y) is characterized in that its elongation at maximum load is 5% or less.

[0069] The inorganic fiber material (Y) used in the fiber-reinforced resin composite material of the present invention is a plurality of inorganic fibers assembled and maintaining a certain or amorphous organizational form of inorganic fibers. By making the elongation at the maximum load of the inorganic fiber material (Y) less than 5%, it is possible to ensure the flame shielding and the strength of withstanding shock waves when constituting the fiber-reinforced resin composite material together with the thermoplastic resin composition (X). It can be considered that the reason is that by making the thermoplastic resin composition (X) moderately impregnated in the inorganic fiber material (Y) and integrated in a manner with an elongation at the maximum load of less than 5%, the mechanical strength is improved, and by forming a dense coke (char) of the phosphorus flame retardant contained in the thermoplastic resin composition (X) in the gap of the fiber organization of the inorganic fiber material (Y), the flame shielding and the strength of withstanding shock waves when contacting the flame can be exerted at the same time.

[0070] From the viewpoint of improving flame shielding properties and strength to withstand shock waves, the elongation of the inorganic fiber material (Y) at maximum load may be 4% or less, 3% or less, or 2% or less. On the other hand, from the viewpoint of facilitating molding processability, it is preferably 0.1% or more.

[0071] In a preferred embodiment, the composite material of the present invention can be a laminate of two or more layers having at least one layer (A) and at least one layer (B), wherein the layer (A) is a layer having a relatively large ratio of the weight of the thermoplastic resin composition (X) per unit area to the weight of the inorganic fiber material (Y), and the layer (B) is a layer having a relatively small ratio of the weight of the thermoplastic resin composition (X) per unit area to the weight of the inorganic fiber material (Y).

[0072] use Figure 1 The layer structure of one embodiment of the fiber-reinforced resin composite material of the present invention will be described.

[0073] like Figure 1 As shown, one embodiment of the fiber-reinforced resin composite material of the present invention comprises at least one layer (A) and at least one layer (B): the layer (A) having a relatively large ratio of the weight of the thermoplastic resin composition (X) to the weight of the inorganic fiber material (Y) per unit area ( Figure 1 11), and a layer (B) ( Figure 1 12) in Figure 1 In the example shown, there are two layers (A), one layer (B), and the layer (B) is sandwiched between the layers (A).

[0074] Such a layer structure can be achieved, for example, by using a sheet formed of an inorganic fiber material (Y) and a sheet formed of a thermoplastic resin composition (X). Figure 2 As shown in FIG. 1 , a laminate 20 is prepared in which a sheet 22 formed of an inorganic fiber material (Y) is sandwiched between two sheets 21 formed of a thermoplastic resin composition (X), and the laminate is pressed from top to bottom at a certain temperature and pressure. The thermoplastic resin composition (X) is melted and impregnated into the sheet 22 formed of the inorganic fiber material (Y). By cooling and solidifying, a layer (A) ( Figure 1 11) sandwiched between layers (B) ( Figure 1The fiber-reinforced resin composite material 10 of one embodiment of the present invention in (12). In the fiber-reinforced resin composite material of the present invention, the above-mentioned layer (A) and layer (B) are formed as separate layers. This is because when the thermoplastic resin composition (X) does not completely impregnate the inorganic fiber material (Y) with an elongation at maximum load of 5% or less, a layer mainly composed of the thermoplastic resin composition (X) will be formed. Therefore, by adjusting the impregnability of the thermoplastic resin composition (X) to the inorganic fiber material (Y), a fiber-reinforced resin composite material having a laminated structure with layers (A) and (B) separated as described above can be produced. In addition, a fiber-reinforced resin composite material formed of a uniform single layer without such separate layers as layer (A) and layer (B) can also be produced.

[0075] The thickness ratio of the above-mentioned layer (A) and layer (B) is preferably in the range of 1 / 99 to 50 / 50. When the thickness ratio is within the above range, the degree of impregnating the thermoplastic resin composition (X) into the inorganic fiber material (Y) can be controlled within an appropriate range, and a fiber-reinforced resin composite material having high flame shielding properties, combustion resistance, and strength against shock waves can be produced. From the above viewpoints, the thickness ratio of layer (A) and layer (B) is more preferably in the range of 2 / 98 to 40 / 60, and further preferably in the range of 5 / 95 to 30 / 70.

[0076] In addition, the weight ratio of the thermoplastic resin composition (X) and the inorganic fiber material (Y) in the entire fiber-reinforced resin composite material (hereinafter referred to as "X / Y") is preferably in the range of 70 / 30 to 20 / 80. The thermoplastic resin composition (X) imparts high flame shielding properties and combustion resistance to the fiber-reinforced resin composite material of the present invention, and the inorganic fiber material (Y) imparts strength against shock waves to the fiber-reinforced resin composite material of the present invention. Their balance is important.

[0077] Therefore, when X / Y is within the above range, a fiber-reinforced resin composite material having high flame shielding properties, combustion resistance, and strength against shock waves can be obtained. From the above viewpoints, X / Y is more preferably in the range of 70 / 30 to 30 / 70, further preferably in the range of 65 / 35 to 30 / 70, still further preferably in the range of 60 / 40 to 30 / 70, and particularly preferably in the range of 60 / 40 to 35 / 65.

[0078] Hereinafter, each component used in the present invention and the obtained fiber-reinforced resin composite material will be described in detail.

[0079] [Thermoplastic resin composition (X)]

[0080] The thermoplastic resin composition (X) of the present invention contains at least (a) a thermoplastic resin and (b) an intumescent flame retardant as a phosphorus-based flame retardant. (a) Thermoplastic resin and (b) phosphorus-based flame retardant (including intumescent flame retardant) are described in detail below.

[0081] <(a) Thermoplastic resin>

[0082] The thermoplastic resin used in the present invention is not particularly limited, and examples thereof include polyolefin resins, polycarbonate resins, polyester resins, acrylonitrile styrene resins, ABS resins, polyamide resins, modified polyphenylene ethers, etc. It should be noted that one or more of them may be used. For example, the thermoplastic resin (a) may be a composite resin of two or more of the thermoplastic resins mentioned above.

[0083] The polyolefin resin is not particularly limited, and the resins described below can be cited. The polyester resin is not particularly limited, and an example thereof is polybutylene terephthalate. The polyamide resin is not particularly limited, and an example thereof is nylon 66 and nylon 6.

[0084] The present invention is particularly useful when at least a polyolefin resin is included as (a) a thermoplastic resin. It should be noted that in the present invention, "polyolefin resin" refers to a resin in which the proportion of olefin units or cycloolefin units is 90 mol% or more relative to 100 mol% of all constituent units constituting the resin.

[0085] The proportion of the olefin unit or the cycloolefin unit relative to 100 mol % of all the structural units constituting the polyolefin resin is preferably 95 mol % or more, particularly preferably 98 mol % or more.

[0086] Examples of polyolefin resins include polyethylene, polypropylene, polybutene, poly(3-methyl-1-butene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene) and other α-olefin polymers; ethylene-propylene block or random copolymers, α-olefin-propylene block or random copolymers having 4 or more carbon atoms, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate copolymers and other α-olefin copolymers; polycyclohexene, polycyclopentene and other cycloolefin polymers. Examples of polyethylene include low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. Examples of polypropylene include isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, and stereoblock polypropylene. Examples of α-olefins having 4 or more carbon atoms in α-olefin-propylene block or random copolymers include butene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene. These polyolefin resins may be used alone or in combination of two or more.

[0087] Among the above-mentioned olefin resins, polypropylene resin (hereinafter sometimes referred to as “PP resin”) is particularly preferred.

[0088] (Melt Flow Rate (MFR))

[0089] The melt flow rate (hereinafter sometimes referred to as MFR) (230°C, 2.16 kg load) of the (a) thermoplastic resin used in the present invention is preferably 40 to 500 g / 10 minutes. When the MFR is 40 g / 10 minutes or more, for example, no defects will occur when the fiber-reinforced resin composite material is press-molded, and the processability will not be reduced. In addition, when it is 500 g / 10 minutes or less, burrs will not be generated in the manufacture of the fiber-reinforced resin composite material (sheet). From the above viewpoints, the MFR is preferably 50 to 400 g / 10 minutes, more preferably 60 to 400 g / 10 minutes, and more preferably 70 to 300 g / 10 minutes.

[0090] The MFR of the (a) thermoplastic resin can be adjusted by, for example, controlling the hydrogen concentration during polymerization.

[0091] In addition, MFR is a value measured according to JIS K7210.

[0092] ((a) Content of thermoplastic resin)

[0093] The content of (a) thermoplastic resin in the fiber-reinforced resin composite material of the present invention is not particularly limited, and is preferably 15 to 80% by mass. When the content of thermoplastic resin is 15% by mass or more, the molding processability becomes particularly good, and the molding of the fiber-reinforced resin composite material becomes easy. On the other hand, when it is 80% by mass or less, a flame retardant, a dispersant and an inorganic fiber can be contained in sufficient amounts to obtain good flame shielding properties. From the above viewpoints, the content of thermoplastic resin in the fiber-reinforced resin composite material is preferably 35 to 70% by mass, and more preferably 40 to 60% by mass.

[0094] <(a-1) Polypropylene resin>

[0095] The (a) thermoplastic resin used in the fiber-reinforced resin composite material of the present invention preferably includes a polypropylene resin. As the polypropylene resin, a propylene homopolymer or a propylene-α-olefin copolymer can be mentioned. Here, the propylene-α-olefin copolymer can be any copolymer of a random copolymer and a block copolymer.

[0096] (α-Olefins)

[0097] As the α-olefin constituting the above-mentioned copolymer, for example, ethylene, 1-butene, 2-methyl-1-propylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, 1-octene, etc. These can be copolymerized with propylene using one kind, and in addition, two or more kinds can be copolymerized with propylene. Among them, from the viewpoint of improving the impact resistance of the fiber-reinforced resin composite material, ethylene or 1-butene having a large effect is preferred, and ethylene is most preferred.

[0098] (Propylene-ethylene random copolymer)

[0099] In the case of a random copolymer of propylene and ethylene, it is preferably composed of 90 to 99.5% by mass, more preferably 92 to 99% by mass of propylene units, and preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass of ethylene units. When the ethylene unit is above the lower limit, sufficient impact strength of the fiber-reinforced resin composite material can be obtained, and when it is below the upper limit, sufficient rigidity can be maintained.

[0100] The contents of propylene units and ethylene units in the random copolymer of propylene and ethylene can be adjusted by controlling the composition ratio of propylene to ethylene during the polymerization of the random copolymer of propylene and ethylene.

[0101] The propylene content of the random copolymer of propylene and ethylene is a value measured using a cross-classifier, FT-IR or the like, and the measurement conditions and the like may be determined by the method described in, for example, JP-A-2008-189893.

[0102] (Melt Flow Rate (MFR))

[0103] The MFR (230°C, 2.16 kg load) of the (a-1) polypropylene resin used in the present invention is preferably 40 to 500 g / 10 minutes. When the MFR is 40 g / 10 minutes or more, no defects will occur when a molded body is obtained by stamping, etc., and the processability will not be reduced. In addition, when it is 500 g / 10 minutes or less, burrs will not be generated in the manufacture of fiber-reinforced resin composite materials. From the above viewpoints, the MFR is preferably 50 to 400 g / 10 minutes, more preferably 60 to 400 g / 10 minutes, and more preferably 70 to 300 g / 10 minutes.

[0104] The MFR of the (a-1) polypropylene-based resin (propylene homopolymer) can be adjusted by controlling the hydrogen concentration during polymerization.

[0105] In addition, MFR is a value measured according to JIS K7210.

[0106] ((a-1) Content of polypropylene resin)

[0107] The content of the (a-1) polypropylene resin in the fiber-reinforced resin composite material of the present invention is not particularly limited, and is preferably 15 to 80% by mass. When the content of the polypropylene resin is 15% by mass or more, the molding processability becomes sufficient, and the molding of the molded body becomes easy. On the other hand, when it is 80% by mass or less, the content of the flame retardant, the dispersant and the inorganic fiber becomes sufficient, and sufficient flame shielding can be obtained. From the above viewpoints, the content of the polypropylene resin in the fiber-reinforced resin composite material is more preferably 35 to 70% by mass, and further preferably 40 to 60% by mass.

[0108] <Modified polyolefin resin>

[0109] The fiber-reinforced resin composite material of the present invention may contain a modified polyolefin resin in addition to the above-mentioned polypropylene resin. Specific examples of the modified polyolefin resin include acid-modified polyolefin resins and hydroxyl-modified polyolefin resins, which may be used alone or in combination.

[0110] It should be noted that the types of the acid-modified polyolefin-based resin and the hydroxy-modified polyolefin-based resin used as the modified polyolefin-based resin are not particularly limited, and any conventionally known modified polyolefin-based resin may be used.

[0111] (Acid-modified polyolefin resin)

[0112] Examples of acid-modified polyolefin resins include resins obtained by graft copolymerizing and chemically modifying polyolefins such as polyethylene, polypropylene, ethylene-α-olefin copolymers, ethylene-α-olefin-non-conjugated diene compound copolymers (EPDM, etc.), and ethylene-aromatic monovinyl compound-conjugated diene compound copolymer elastomers using unsaturated carboxylic acids such as maleic acid or maleic anhydride.

[0113] The graft copolymerization can be carried out by reacting the polyolefin with an unsaturated carboxylic acid in a suitable solvent using a free radical generator such as benzoyl peroxide. In addition, the unsaturated carboxylic acid or its derivative component can also be introduced into the polymer chain by random or block copolymerization with a polyolefin monomer.

[0114] Examples of the unsaturated carboxylic acid used for modification include compounds having a polymerizable double bond into which a carboxyl group and, if necessary, a hydroxyl group, an amino group or the like are introduced, such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.

[0115] Derivatives of unsaturated carboxylic acids include anhydrides, esters, amides, imides, metal salts, etc., and specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, etc. Among them, maleic anhydride is preferred.

[0116] Preferred acid-modified polyolefin resins include resins modified by grafting maleic anhydride with an olefin polymer having ethylene and / or propylene as main polymer constituent units, resins modified by copolymerizing an olefin having ethylene and / or propylene as main components with maleic anhydride, etc. Specifically, combinations of polyethylene / maleic anhydride grafted ethylene-butene-1 copolymers, or combinations of polypropylene / maleic anhydride grafted polypropylene, etc. may be mentioned.

[0117] (Hydroxy-modified polyolefin resin)

[0118] The hydroxy-modified polyolefin resin is a modified polyolefin resin containing a hydroxy group. The hydroxy-modified polyolefin resin may have a hydroxy group at an appropriate position, for example, at the terminal of the main chain or at a side chain.

[0119] Examples of the olefin resin constituting the hydroxy-modified polyolefin resin include single products or copolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, and dodecene, and copolymers of the above α-olefins and copolymerizable monomers.

[0120] Preferred hydroxy-modified polyolefin resins include, for example, low-density, medium-density or high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, ethylene-(methyl)acrylate copolymers, ethylene-vinyl acetate copolymers and other hydroxy-modified polyethylene resins, polypropylene homopolymers such as isotactic polypropylene, random copolymers of propylene and α-olefins (such as ethylene, butene, hexane, etc.), propylene-α-olefin block copolymers, and hydroxy-modified polypropylene resins such as hydroxy-modified poly(4-methylpentene-1).

[0121] <(b) Phosphorus flame retardants>

[0122] The fiber-reinforced resin composite material of the present invention contains (b) a phosphorus-based flame retardant. The phosphorus-based flame retardant is preferred from the viewpoint of improving flame barrier properties, having no bioresidual property, and having excellent flame retardancy.

[0123] Furthermore, from the viewpoint of improving flame barrier properties, the fiber-reinforced resin composite material of the present invention contains an intumescent flame retardant as the phosphorus-based flame retardant.

[0124] Intumescent flame retardants are flame retardants that inhibit the combustion of materials by forming a surface expansion layer (intumescent) that prevents the diffusion of radiant heat, combustion gas, smoke, etc. from the combustion source from the combustion product to the outside. Examples of intumescent flame retardants include salts of (poly)phosphoric acid and nitrogen compounds. Examples of nitrogen compounds include ammonia, melamine, piperazine, and other nitrogen compounds described below.

[0125] Specifically, ammonium salts and amine salts of (poly)phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate are mentioned. Among them, compounds having a melamine structure or a piperazine structure are particularly preferred.

[0126] In addition, examples of nitrogen compounds include ammonia, melamine, piperazine, and other nitrogen compounds. Examples of other nitrogen compounds include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediol, N,N'-dimethylethylenediamine, N ... diamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine , 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3 ,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine, cyanuric acid diamide, benzoguanamine, acetoguanamine, o-phthaloguanamine, melamine isocyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexamethylene dimelamine, etc.

[0127] Intumescent flame retardants are salts of (poly)phosphoric acid and nitrogen compounds, which form foamed charred products, i.e., surface intumescent layers, when the resin composition burns. The formation of the surface intumescent layer can inhibit the diffusion and heat transfer of decomposition products, thus exhibiting excellent flame retardancy.

[0128] Examples of commercially available intumescent flame retardants include ADK STAB FP-2100J, FP-2200, and FP-2500S (manufactured by ADEKA Corporation).

[0129] It should be noted that, in the present invention, an intumescent flame retardant is essential, but other flame retardants may also be used in combination, specifically phosphorus flame retardants other than intumescent flame retardants (hereinafter sometimes referred to as "other phosphorus flame retardants"), bromine flame retardants, antimony flame retardants, etc.

[0130] (Other phosphorus flame retardants)

[0131] The phosphorus-based flame retardant is a phosphorus compound, that is, a compound containing a phosphorus atom in a molecule. The phosphorus-based flame retardant forms a char when the resin composition is burned, thereby exhibiting a flame retardant effect.

[0132] The phosphorus flame retardant may be a known phosphorus flame retardant, for example, (poly)phosphate, (poly)phosphate ester, etc. Here, "(poly)phosphate" means a phosphate or a polyphosphate, and "(poly)phosphate ester" means a phosphate ester or a polyphosphate ester.

[0133] It should be noted that the phosphorus-based flame retardant is preferably solid at 80°C.

[0134] As the phosphorus-based flame retardant, (poly)phosphate is preferred from the viewpoint of flame retardancy.

[0135] Examples of the (poly)phosphate include ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, and melamine orthophosphate. Examples of other phosphorus flame retardants include calcium phosphate and magnesium phosphate.

[0136] In the above examples, compounds obtained by replacing melamine or piperazine with other nitrogen compounds can also be used in the same manner. These (poly)phosphates may be used alone or in combination of two or more.

[0137] (Brominated flame retardants)

[0138] Examples of the bromine-based flame retardant include decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, 1,2-bis(2',3',4',5',6'-pentabromophenyl)ethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, 2,6-dibromophenol, 2,4-dibromophenol, brominated polystyrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate, 2,2-bis[4'(2'',3''-dibromopropoxy)-3',5'-dibromophenyl]-propane, bis[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfone, and tris(2,3-dibromopropyl)isocyanurate.

[0139] (Antimony flame retardant)

[0140] Examples of the antimony flame retardant include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, antimony trichloride, antimony trisulfide, antimony oxychloride, antimony dichloride perchloropentane, and potassium antimonate. Antimony trioxide and antimony pentoxide are particularly preferred.

[0141] Among the above flame retardants, halogen-free flame retardants are preferred from the viewpoint of environmental friendliness.

[0142] In addition, the above flame retardants may be used alone or in combination of two or more.

[0143] ((b) Content of phosphorus flame retardant)

[0144] The content of the phosphorus flame retardant (including intumescent flame retardant) in the fiber-reinforced resin composite material of the present invention is not particularly limited, and as the content in the thermoplastic resin composition (X), it is preferably in the range of 1 to 30% by mass. When it is 1% by mass or more, it is possible to impart good flame retardancy to the fiber-reinforced resin composite material, and good flame shielding properties can be obtained. On the other hand, when the phosphorus flame retardant is 30% by mass or less, it is possible to contain the thermoplastic resin with a sufficient content ratio, so that the molding processability becomes better. From the above viewpoints, the content of the flame retardant in the thermoplastic resin composition (X) is more preferably in the range of 1 to 25% by mass, and further preferably in the range of 3 to 20% by mass.

[0145] <(c) Dispersant>

[0146] As (c) dispersant, as long as (b) phosphorus flame retardant can be dispersed in (a) thermoplastic resin, there is no particular limitation, and from the aspect of compatibility with (a) thermoplastic resin, polymer dispersant can be suitably used. Preferably, a dispersant that can disperse (b) phosphorus flame retardant in (a-1) polypropylene resin is suitably used. As polymer dispersant, polymer dispersant with functional groups is preferably used, and from the aspect of dispersion stability, polymer dispersant with functional groups such as carboxyl, phosphoric acid, sulfonic acid, primary, secondary or tertiary amino, quaternary ammonium salt, and groups from nitrogen-containing heterocyclic rings such as pyridine, pyrimidine, and pyrazine is preferably used.

[0147] In the present invention, a polymer dispersant having a carboxyl group is preferred, and in particular, when a suitable phosphorus flame retardant is used as the flame retardant, a copolymer of an α-olefin and an unsaturated carboxylic acid is preferred. By using the dispersant, the dispersibility of the phosphorus flame retardant can be improved, and the content of the flame retardant can be reduced.

[0148] (Copolymer of α-olefin and unsaturated carboxylic acid)

[0149] The ratio of the α-olefin unit in the total of 100 mol % of the α-olefin unit and the unsaturated carboxylic acid unit in the "copolymer of α-olefin and unsaturated carboxylic acid" (hereinafter referred to as "copolymer (c1)") of the present invention is preferably 20 mol % to 80 mol %.

[0150] In the copolymer (c1), the ratio of the α-olefin unit to the total amount of the α-olefin unit and the unsaturated carboxylic acid unit is more preferably 30 mol% or more, and on the other hand, it is more preferably 70 mol% or less. When the ratio of the α-olefin is above the above lower limit, the compatibility with the (a) polyolefin resin becomes better, and when it is below the above upper limit, the compatibility with the (b) phosphorus flame retardant becomes better.

[0151] In the copolymer (c1), the α-olefin is preferably an α-olefin having 5 or more carbon atoms, and more preferably an α-olefin having 10 or more and 80 or less carbon atoms. When the carbon number of the α-olefin is 5 or more, there is a tendency for the compatibility with the thermoplastic resin (a) to become better, and when it is 80 or less, it is advantageous from the perspective of raw material cost. From the above viewpoints, the carbon number of the α-olefin is more preferably 12 or more and 70 or less, and particularly preferably 18 or more and 60 or less.

[0152] In the copolymer (c1), unsaturated carboxylic acids include, for example, (meth)acrylic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, tetrahydrophthalic acid, itaconic acid, crotonic acid, isocrotonic acid, glutaconic acid, norbornyl-5-ene-2,3-dicarboxylic acid, and esters, anhydrides, and imides of these unsaturated carboxylic acids. It should be noted that "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0153] Specific examples of esters, anhydrides or imides of unsaturated carboxylic acids include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and glycidyl (meth)acrylate; dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride; maleimide compounds such as maleimide, N-ethylmaleimide, and N-phenylmaleimide, etc. These may be used alone or in combination of two or more.

[0154] Among the above, esters and dicarboxylic anhydrides are preferred from the viewpoint of copolymerization reactivity. Among them, dicarboxylic anhydrides are preferred from the viewpoint of compatibility with phosphorus-based flame retardants suitable as flame retardants, and maleic anhydride is particularly preferred.

[0155] The weight average molecular weight of the copolymer (c1) is preferably 2000 or more, more preferably 3000 or more, and is preferably 50000 or less, more preferably 30000 or less. When the weight average molecular weight of the copolymer (c1) is within the above range, the dispersibility of the (b) phosphorus-based flame retardant is further improved.

[0156] The weight average molecular weight of the copolymer (c1) is a value calculated in terms of standard polystyrene obtained by dissolving the copolymer (c1) in tetrahydrofuran (THF) and measuring the result by gel permeation chromatography.

[0157] Examples of commercially available products of the copolymer (c1) include Licolub CE2 (manufactured by CLARIANT JAPAN) and DIACARNA 30M (manufactured by Mitsubishi Chemical Corporation).

[0158] The content of the (c) dispersant in the thermoplastic resin composition (X) of the present invention is greater than 0 and 25 parts by mass or less, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the (b) phosphorus flame retardant.

[0159] According to the research of the present inventors, by using thermoplastic resin as matrix resin and making phosphorus flame retardant uniformly dispersed and present in inorganic fibers constituting fiber-reinforced resin composite materials, the flame shielding property of fiber-reinforced resin composite materials can be significantly improved. The detailed mechanism is not clear, but the present inventors speculate as follows. That is, in the case where the flame retardant is uniformly dispersed in the resin between inorganic fibers, the char formed by the flame retardant contacting the flame is fixed to the gap between the inorganic fibers. Further, the size of the char formed by expanding and forming when contacting the flame is limited by the gap between the inorganic fibers, and thus, the size of the char formed becomes uniform. It can be considered that by combining the fixing effect of the char based on inorganic fibers with the homogenization of the size of the char, a dense char can be formed, which significantly improves the flame shielding property of fiber-reinforced resin composite materials. Based on these insights, the present inventors found that by setting the ratio of the content of the dispersant to the flame retardant to a specific range, it is possible to control so that the flame retardant is uniformly present in the resin between the inorganic fibers, which can significantly improve the flame shielding property of fiber-reinforced resin composite materials.

[0160] Based on the above reasons, when the content of (c) dispersant is greater than 0, the dispersibility of (b) phosphorus flame retardant becomes sufficient, and sufficient flame shielding can be given to the fiber-reinforced resin composite material. On the other hand, when it is less than 25 parts by mass, the physical properties of the fiber-reinforced resin composite material become sufficient. From the same point of view, the content of (c) dispersant is preferably more than 0.01 parts by mass, more preferably more than 0.1 parts by mass, further preferably more than 1 parts by mass, and particularly preferably more than 2 parts by mass. On the other hand, about the upper limit value, it is more preferably less than 20 parts by mass, more preferably less than 15 parts by mass, further more preferably less than 10 parts by mass, further more preferably less than 5 parts by mass, and particularly preferably less than 3 parts by mass.

[0161] In addition, the ratio of (c) dispersant to a total of 100 parts by mass of (a) thermoplastic resin and (b) phosphorus flame retardant is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, further preferably 2.0 parts by mass or less, further preferably 1.5 parts by mass or less, and further preferably 1.0 parts by mass or less. When the ratio of (c) dispersant is above the lower limit, (b) phosphorus flame retardant is more well dispersed, and the flame shielding property, physical properties, and appearance of the obtained molded body of the obtained fiber-reinforced resin composite material become better. When the ratio of (c) dispersant is below the upper limit, the influence of (c) dispersant on the flame shielding property of the fiber-reinforced resin composite material can be further suppressed. In particular, the ratio of (c) dispersant to a total of 100 parts by mass of polyolefin resin and (b) phosphorus flame retardant is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, further preferably 2.0 parts by mass or less, further preferably 1.5 parts by mass or less, further preferably 1.0 parts by mass or less.

[0162] In addition, for the inorganic fiber fabric as the inorganic fiber material (Y) described in detail below, the proportion of the (c) dispersant relative to 100 parts by mass of the inorganic fiber constituting the inorganic fiber fabric is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and further preferably 2.0 parts by mass or less. When the proportion of the (c) dispersant is above the above lower limit, the flame shielding properties, physical properties, and appearance of the obtained molded body of the obtained fiber-reinforced resin composite material become better. When the proportion of the (c) dispersant is below the above upper limit, the influence of the (c) dispersant on the flame shielding properties of the fiber-reinforced resin composite material can be further suppressed.

[0163] <Inorganic fiber material (Y)>

[0164] The fiber-reinforced resin composite material of the present invention contains an inorganic fiber material (Y). The inorganic fiber material (Y) is a tissue of inorganic fibers in which a plurality of inorganic fibers are assembled and a certain or amorphous tissue morphology is maintained. In addition, the elongation of the inorganic fiber material (Y) at maximum load is less than 5%.

[0165] Specific examples of the inorganic fiber material having such an elongation at the maximum load include inorganic fiber fabrics.

[0166] The inorganic fiber fabric is a fabric composed of longitudinal and transverse threads formed by inorganic fibers. The fabric structure is not particularly limited, and can be any structure such as plain weave, twill weave, satin weave, etc. For the fabric, the gap between the fiber bundles constituting the longitudinal threads of the fabric and the gap between the transverse thread bundles are preferably 0.5 mm or less, respectively. When the gap is 0.5 mm or less, high flame shielding properties can be obtained.

[0167] As inorganic fibers constituting the inorganic fiber material (Y), various fibers can be used, for example: glass fiber, rock wool, alumina fiber, metal oxide fibers such as silica alumina fiber, potassium titanate fiber, calcium silicate (wollastonite) fiber, ceramic fibers such as ceramic fiber, carbon fiber, metal fiber, etc. These inorganic fibers can be used alone or in combination of two or more.

[0168] Among the above-mentioned inorganic fibers, at least one selected from glass fibers and alumina fibers is preferred from the viewpoint of flame shielding properties and processability.

[0169] As the above-mentioned inorganic fiber, two or more inorganic fibers with different melting temperatures may be included. As a combination of two or more inorganic fibers with different melting temperatures, it is preferred that at least one is glass fiber and the other one or more is a combination of one or more inorganic fibers selected from alumina fiber, silica fiber, alkaline earth silicate fiber (biosoluble) and carbon fiber. By including two or more inorganic fibers with different melting temperatures, it is possible to effectively prevent the flame shielding function from being reduced.

[0170] In addition, the inorganic fibers used in the present invention may be used in combination with a sizing agent or a surface treatment agent. Examples of such sizing agents or surface treatment agents include compounds having functional groups such as epoxy compounds, silane compounds, and titanate compounds.

[0171] The average fiber diameter of the inorganic fibers is preferably 3 to 25 μm, and the average fiber length is preferably 0.1 mm or more, more preferably 1 mm or more, and even more preferably 5 mm or more.

[0172] It should be noted that the suitable ranges of the average fiber diameter and the average fiber length vary depending on the type of inorganic material constituting the inorganic fibers, and the specific suitable ranges will be described later.

[0173] In addition, the fiber diameter can be measured using a scanning electron microscope, etc., and the average fiber diameter can be obtained by, for example, randomly measuring the fiber diameters of 10 fibers and calculating the average value. In addition, the fiber length can be measured using a ruler, a vernier caliper, etc. from an image magnified by a microscope as needed, and the average fiber length can be obtained by, for example, randomly measuring the fiber lengths of 10 fibers and calculating the average value.

[0174] The content of the inorganic fiber material in the fiber-reinforced resin composite material of the present invention is 1 to 80% by mass. When the content of the inorganic fiber material is 1% by mass or more, the strength, rigidity and impact resistance of the fiber-reinforced resin composite material are sufficient, and when it is 80% by mass or less, it is preferred from the perspective of manufacturing and processing of the fiber-reinforced resin composite material. In addition, when the content of the inorganic fiber is 80% by mass or less, the specific gravity of the fiber-reinforced resin composite material is reduced, and the lightweight effect as a metal substitute is obvious.

[0175] From the above viewpoints, the content of the inorganic fiber material (Y) in the fiber-reinforced resin composite material is preferably 3 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 30 to 45% by mass.

[0176] (Fiberglass)

[0177] As one of the inorganic fibers suitable for the fiber-reinforced resin composite material of the present invention, glass fiber can be cited. As the glass fiber, for example, it can be a long fiber with an average fiber length of 30 mm or more, or it can be a fiber with a short average fiber length (chopped strands). From the viewpoints of flame shielding, rigidity, impact resistance, etc., it is preferred to use glass fibers with a long average fiber length.

[0178] More specifically, the average fiber length is preferably 5 mm or more. When the average fiber length is 5 mm or more, the strength and impact resistance of the fiber-reinforced resin composite material become good. From the above viewpoints, the average fiber length of the glass fiber is preferably 5 mm or more, and more preferably 30 mm or more.

[0179] It should be noted that there is no particular upper limit on the average fiber length of the glass fiber. For example, in the case of particles produced by using glass fibers through pultrusion, the length of the particles becomes the fiber length of the glass fibers, so the maximum is about 20 mm. In addition, in swirl mats using long glass fibers, the length of the glass fibers in the roving used for production becomes the maximum fiber length, so it will reach about 17000 m (17 km), but in the case of cutting according to the size of the fiber-reinforced resin composite material, the length after cutting becomes the maximum fiber length.

[0180] In addition, the average fiber diameter of the glass fiber is preferably in the range of 9 to 25 μm. When the average fiber diameter is 9 μm or more, the rigidity and impact resistance of the fiber-reinforced resin composite material become sufficient, while on the other hand, when the average fiber diameter is 25 μm or less, the strength of the fiber-reinforced resin composite material becomes good. From the above viewpoints, the average fiber diameter of the glass fiber is more preferably in the range of 10 to 15 μm.

[0181] In addition, the average fiber diameter and the average fiber length of the glass fiber can be measured by the above-mentioned method.

[0182] The material of the glass fiber used in the present invention is not particularly limited, and may be any of alkali-free glass, low-alkali glass, and alkali-containing glass, and materials of various compositions conventionally used as glass fibers may be used.

[0183] (Alumina Fiber)

[0184] As one of the inorganic fibers suitable for the fiber-reinforced resin composite material of the present invention, alumina fiber can be cited. Alumina fiber is generally a fiber formed of alumina and silica, and in the fiber-reinforced resin composite material of the present invention, the composition ratio (mass ratio) of alumina / silica of the alumina fiber is preferably in the range of 65 / 35 to 98 / 2, which is called a mullite composition or a high alumina composition, more preferably in the range of 70 / 30 to 95 / 5, and particularly preferably in the range of 70 / 30 to 74 / 26.

[0185] The average fiber diameter of the alumina fibers is preferably in the range of 3 to 25 μm, and preferably substantially no fibers with a fiber diameter of 3 μm or less are included. Here, substantially no fibers with a fiber diameter of 3 μm or less means that fibers with a fiber diameter of 3 μm or less account for less than 0.1% by mass of the total inorganic fiber mass.

[0186] In addition, the average fiber diameter of the alumina fiber is more preferably 5 to 8 μm. If the average fiber diameter of the inorganic fiber is too thick, the resilience and toughness of the mat-shaped inorganic fiber assembly layer will decrease. On the contrary, if it is too thin, the amount of dust floating in the air will increase, and the probability of containing inorganic fibers with a fiber diameter of 3 μm or less will increase.

[0187] The alumina fibers preferably have an average fiber length of 5 mm or more, more preferably 30 mm or more, and even more preferably 50 mm or more. 3 mm or less, more preferably 1.0×10 3 When the average fiber length and average fiber diameter of the alumina fibers are within this range, the strength and impact resistance of the fiber-reinforced resin composite material become good.

[0188] (Carbon Fiber)

[0189] The suitable range of carbon fiber is also the same as that of glass fiber.

[0190] <Optional Additives>

[0191] The fiber-reinforced resin composite material of the present invention may contain any additional components in addition to the above components, within a range that does not significantly impair the effects of the present invention, for the purpose of further improving the effects of the present invention or imparting other effects.

[0192] Specifically, the colorants include pigments, light stabilizers such as hindered amines, ultraviolet absorbers such as benzotriazoles, nucleating agents such as sorbitols, antioxidants such as phenols and phosphorus, antistatic agents such as nonionic surfactants, neutralizing agents such as inorganic compounds, antibacterial / antifungal agents such as thiazoles, halogen compounds, flame retardants / flame retardant aids such as lignophenol, plasticizers, dispersants such as organic metal salts, lubricants such as fatty acid amides, metal deactivators such as nitrogen compounds, thermoplastic resins such as polyolefin resins other than the above-mentioned polypropylene resins, polyamide resins, and polyester resins, and elastomers (rubber components) such as olefin elastomers and styrene elastomers.

[0193] These optional additional components may be used in combination of two or more.

[0194] Colorants such as inorganic and organic pigments are effective for imparting or improving the colored appearance, aesthetics, feel, commercial value, weather resistance, durability, etc. of the polypropylene resin composition and its molded article.

[0195] As specific examples, inorganic pigments include carbon black such as furnace carbon and ketjen carbon; titanium oxide; iron oxide (red iron, etc.); chromic acid (chrome yellow, etc.); molybdic acid; selenium sulfide; ferrocyanide, etc., and organic pigments include azo pigments such as poorly soluble azo lakes, soluble azo lakes, insoluble azo chelates; condensed azo chelates; other azo chelates; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; threne pigments such as anthraquinone, perinone, perylene, and thioindigo; dye lakes; quinacridones; diazine; Oxazine; isoindolinone, etc. In addition, in order to make a metallic style or a pearl style, aluminum flakes and pearl pigments may be contained. In addition, dyes may also be contained.

[0196] Light stabilizers and ultraviolet absorbers, such as hindered amine compounds, benzotriazoles, benzophenones, salicylates, etc., are effective in imparting and improving the weather resistance and durability of polypropylene resin compositions and their molded products, and are effective in further improving weather resistance and discoloration.

[0197] As specific examples, hindered amine compounds include condensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine; poly[[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]]; 1,2,3,4-butanetetracarboxylic acid tetra(2,2,6,6-tetramethyl-4-piperidyl) ester; 1,2,3,4-butanetetracarboxylic acid tetra(1,2,2,6,6-pentamethyl-4-piperidyl) ester; decanetetracarboxylic acid tetra(1,2,2,6,6-pentamethyl-4-piperidyl) ester; Examples of the benzotriazoles include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole. Examples of the benzophenones include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone. Examples of the salicylic acid esters include 4-tert-butylphenyl salicylate and 2,4-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoate.

[0198] Here, a method of using the above-mentioned light stabilizer and ultraviolet absorber in combination is preferred because it has a significant effect of improving weather resistance, durability, weather resistance and discoloration.

[0199] As antioxidants, for example, phenolic, phosphorus, and sulfur antioxidants are effective for imparting or improving heat resistance stability, processing stability, heat aging resistance, and the like of polypropylene resin compositions and molded articles thereof.

[0200] In addition, as the antistatic agent, for example, nonionic, cationic or other antistatic agents are effective for imparting or improving the antistatic property of the polypropylene resin composition and its molded article.

[0201] As olefin elastomers, for example, there can be mentioned: ethylene / α-olefin copolymer elastomers such as ethylene / propylene copolymer elastomer (EPR), ethylene-butene copolymer elastomer (EBR), ethylene / hexene copolymer elastomer (EHR), ethylene / octene copolymer elastomer (EOR); ethylene / α-olefin / diene terpolymer elastomers such as ethylene / propylene / ethylidene norbornene copolymer, ethylene / propylene / butadiene copolymer, ethylene / propylene / isoprene copolymer; styrene / butadiene / styrene triblock copolymer elastomer (SBS), etc.

[0202] In addition, examples of styrene-based elastomers include styrene / isoprene / styrene triblock copolymer elastomers (SIS), styrene-ethylene / butylene copolymer elastomers (SEB), styrene-ethylene / propylene copolymer elastomers (SEP), styrene-ethylene / butylene-styrene copolymer elastomers (SEBS), styrene-ethylene / butylene-ethylene copolymer elastomers (SEBC), hydrogenated styrene / butadiene elastomers (HSBR), styrene-ethylene / propylene-styrene copolymer elastomers (SEPS), styrene-ethylene / ethylene / propylene-styrene copolymer elastomers (SEEPS), styrene-butadiene / butylene-styrene copolymer elastomers (SBBS), partially hydrogenated styrene-isoprene-styrene copolymer elastomers, partially hydrogenated styrene-isoprene / butadiene-styrene copolymer elastomers and the like, and hydrogenated polymer-based elastomers such as ethylene-ethylene / butylene-ethylene copolymer elastomers (CEBC) and the like.

[0203] Among them, when an ethylene-octene copolymer elastomer (EOR) and / or an ethylene-butene copolymer elastomer (EBR) is used, it is preferred for the polypropylene-based resin composition of the present invention and its molded article because it is easy to impart appropriate flexibility and tends to have excellent impact resistance.

[0204] <Method for producing thermoplastic resin composition (X)>

[0205] As described above, the thermoplastic resin composition (X) of the present invention contains (a) a thermoplastic resin, a modified polyolefin resin added as needed, (b) a phosphorus flame retardant, and (c) a dispersant added as needed. In addition, any additional components may be further formulated. In the above-mentioned thermoplastic resin composition (X), when (a) the thermoplastic resin is (a-1) a polypropylene resin, it is sometimes specifically referred to as a polypropylene resin composition (hereinafter sometimes described as a "PP composition").

[0206] As a method for producing the thermoplastic resin composition (X) or the PP composition, a conventionally known method can be utilized, and the composition can be produced by blending the above-mentioned components, mixing, and melt-kneading.

[0207] Mixing can be performed using a mixer such as a tumbler, a V mixer, or a ribbon mixer, and melt kneading can be performed using a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender mixer, a kneader, or the like to perform melt kneading and granulation.

[0208] <Method for producing fiber-reinforced resin composite material>

[0209] The method for producing the fiber-reinforced resin composite material of the present invention is not particularly limited, but it is preferably produced by impregnating the above-mentioned thermoplastic resin composition (X) or PP composition into a mat formed of an inorganic fiber material (Y) (hereinafter sometimes referred to as "inorganic fiber mat (Y')"). As the impregnation method, there are the following methods: a method of applying a thermoplastic resin composition or PP composition to an inorganic fiber mat (Y'); a method of pre-preparing a sheet of a thermoplastic resin composition or PP composition (hereinafter sometimes referred to as "thermoplastic resin sheet" or "PP sheet"), laminating the thermoplastic resin sheet or PP sheet on the inorganic fiber mat (Y'), heating it, melting it, and impregnating it, etc.

[0210] In the present invention, from the viewpoint of the impregnation of the fiber into the fiber reinforced resin composite material, a method of laminating a thermoplastic resin sheet or PP sheet on a mat formed of an inorganic fiber material, heating and melting the sheet is preferred. In particular, the sheet can be obtained by laminating the sheet so that the inorganic fiber mat is located between two thermoplastic resin sheets or PP sheets, then heating and pressurizing the laminate, and then cooling and solidifying the laminate.

[0211] Here, the thickness of the thermoplastic resin sheet or the PP sheet is not particularly limited as long as it is within a range that allows the inorganic fiber mat to be impregnated satisfactorily.

[0212] (Inorganic fiber mat (Y'))

[0213] The form of the inorganic fiber material used in the method for producing a fiber-reinforced resin composite material is not particularly limited, and various forms can be used, but it is preferably formed into a mat-like or sheet-like form.

[0214] More specifically, a woven fabric made of glass fibers (hereinafter referred to as “glass fiber woven fabric”) or a woven fabric made of metal oxide fibers such as alumina fibers (hereinafter referred to as “metal oxide woven fabric”) is preferred.

[0215] The weight per unit area (mass per unit area) of the inorganic fiber mat is not particularly limited and can be appropriately determined according to the intended use, but is preferably 300 g / m 2 More than 800 g / m 2 , more preferably greater than 1500g / m 2 In addition, the weight per unit area of ​​the inorganic fiber mat is not particularly limited, but is preferably 5000 g / m 2 Below, more preferably 4500g / m 2 Below, more preferably 4000g / m 2 Below, particularly preferably 3500g / m 2 the following.

[0216] The thickness of the inorganic fiber mat of the present invention is not particularly limited, but is preferably 4 mm or more, more preferably 5 mm or more, and further preferably 6 mm or more. In addition, the thickness of the inorganic fiber mat is preferably 40 mm or less, further preferably 35 mm or less, and particularly preferably 30 mm or less.

[0217] In the method of laminating a thermoplastic resin sheet or a PP sheet on an inorganic fiber mat, heating and melting it, the heating temperature is preferably 170 to 300°C. When the heating temperature is 170°C or higher, the fluidity of the polypropylene resin is sufficient, and the PP composition can be fully impregnated into the inorganic fiber mat, and a suitable fiber-reinforced resin composite material can be obtained. On the other hand, when the heating temperature is 300°C or lower, the thermoplastic resin composition or the PP composition does not deteriorate.

[0218] In addition, the pressurization pressure is preferably 0.1 to 1 MPa. When the pressurization pressure is 0.1 MPa or more, the thermoplastic resin composition or PP composition can be fully impregnated into the inorganic fiber mat, and a suitable fiber-reinforced resin composite material can be obtained. On the other hand, by setting it to 1 MPa or less, the thermoplastic resin composition or PP composition flows and burrs are not generated.

[0219] In addition, the cooling temperature is not particularly limited as long as it is below the solidification point of the thermoplastic resin in the thermoplastic resin composition or the PP composition. When the cooling temperature is 80° C. or below, the obtained fiber-reinforced resin composite material will not be deformed when taken out. From the above viewpoints, the cooling temperature is preferably room temperature to 80° C.

[0220] As methods for obtaining a fiber-reinforced resin composite material by heating, pressurizing and cooling the above-mentioned laminate, there are the following methods: a method of press-molding the laminate in a mold with a heating device; and a lamination process in which the laminate is heated and pressurized by passing it between two pairs of rollers with a heating device. In particular, the lamination process is preferred because it can be produced continuously and therefore has good productivity.

[0221] <Thickness of fiber-reinforced resin composite materials>

[0222] The fiber-reinforced resin composite material of the present invention has a thickness of usually 1 to 10 mm, preferably 2 to 5 mm. When the fiber-reinforced resin composite material has a thickness of 1 mm or more, the fiber-reinforced resin composite material can be easily manufactured. On the other hand, when the fiber-reinforced resin composite material has a thickness of 10 mm or less, when the fiber-reinforced resin composite material is processed by press molding or the like, long-term preheating is not required, and good molding processability can be obtained.

[0223] <Molding body>

[0224] The fiber-reinforced resin composite material of the present invention can be molded into a desired shape by press molding according to a conventional method, and a molded body composed of the fiber-reinforced resin composite material can be obtained.

[0225] (use)

[0226] As the use of the fiber-reinforced resin composite material of the present invention, for example, various parts in industrial fields such as automobile parts and electrical and electronic equipment parts can be mentioned. In particular, since it is excellent in strength, rigidity, conductivity, and processability, it can be suitably used in applications that require these properties to be more highly balanced, such as various housings and frames such as battery housings.

[0227] [Structure]

[0228] As the structure of the present invention, it is preferred that the battery has a battery casing and a battery cell, and the battery is not particularly limited. For example, secondary batteries such as lithium-ion batteries, nickel / hydrogen batteries, lithium / sulfur batteries, nickel / cadmium batteries, nickel / iron batteries, nickel / zinc batteries, sodium / sulfur batteries, lead storage batteries, and air batteries can be cited. Among them, lithium-ion batteries are preferred, and in particular, the battery casing of the present invention can be suitably used to suppress thermal runaway of lithium-ion batteries. That is, the battery casing of the present invention is preferably a battery casing of a lithium-ion battery.

[0229] [Electric vehicles]

[0230] The electric vehicle of the present invention refers to a transportation device such as a vehicle, a ship, or an airplane that runs on electricity as an energy source. It should be noted that the vehicle includes not only electric vehicles (EVs) but also hybrid vehicles.

[0231] A structure such as a battery having the battery case and the battery cell of the present invention is highly safe and is very useful for electric vehicles using a battery module with an increased energy density in order to extend the driving distance.

[0232] Example

[0233] Hereinafter, the present invention will be described in detail using Examples, but the present invention is not limited to these Examples.

[0234] 1. Evaluation of flame shielding properties

[0235] The fiber-reinforced resin composite materials prepared in each example and comparative example were exposed to a 1300°C burner flame from one surface and evaluated for whether the flame penetrated after 15 minutes. The distance from the burner nozzle to the sample was set to 160 mm, and the flame surface was set to 1200°C. The flame surface temperature was confirmed by a thermocouple thermometer.

[0236] 2. Air jet test (strength to withstand shock waves)

[0237] The fiber-reinforced resin composite materials prepared in each example and comparative example were exposed to a 1200°C burner flame from one surface in the same manner as in the above flame shielding property evaluation. After 15 minutes, air was blown at a pressure of 0.2 MPa to evaluate whether holes were penetrated.

[0238] In addition, the blowing conditions of air are as follows.

[0239] Spray pressure: 0.2MPa

[0240] Spray diameter: inner diameter φ3.0mm

[0241] Distance from sample to air nozzle: 35mm

[0242] Air injection position: The part of the burner that contacts the flame

[0243] 3. Evaluation of flammability

[0244] The fiber-reinforced resin composite materials prepared in each example and comparative example were evaluated for flame retardancy based on the UL94 50W (20 mm) vertical burning test. The evaluation was based on whether V-1 was achieved.

[0245] 4. Puncture test

[0246] The fiber-reinforced resin composite material prepared in each example was heated at 1200°C for 15 minutes. For the heated fiber-reinforced composite material, the maximum impact force, maximum impact energy, and displacement at the maximum impact point when the test piece was punched were measured using a high-speed puncture impact tester HYDROSHOT (HITS-P10) manufactured by Shimadzu Corporation. The impactor diameter was set to 1 / 2 inch, the test piece support table was set to 50 mm, and the test speed was set to 3 m / s. The area of ​​the displacement-load curve obtained in the test was evaluated as the maximum impact energy of the test piece. The measurement was carried out in an indoor environment with a temperature of 23±2°C and a humidity of 50±10%.

[0247] 5. AUTOGRAPH test

[0248] The fiber-reinforced resin composite material prepared in each example was heated at 1200°C for 15 minutes. The penetration strength of the central portion of the heated fiber-reinforced resin composite material (200×200 mm) was measured at a test speed of 20 mm / min using an AUTOGRAPH "AG-10TA" (manufactured by Shimadzu Corporation) with a φ20 mm (front end R3 mm) pressing fixture.

[0249] (Materials used)

[0250] 1. Polypropylene resin (component a)

[0251] “NOVATEC PP SA06GA” (melt flow rate: 60 g / 10 minutes) manufactured by Japan Polypropylene Co., Ltd. was used.

[0252] 2. Phosphorus flame retardant (component b)

[0253] The phosphorus-based flame retardant composition (ADK STAB FP-2500S manufactured by ADEKA Corporation, containing 50-60% by mass of piperazine pyrophosphate, 35-45% by mass of melamine pyrophosphate, and 3-6% by mass of zinc oxide) is used.

[0254] 3. Dispersant (component C)

[0255] α-Olein / maleic anhydride copolymer (manufactured by Mitsubishi Chemical Corporation, DIACANNA 30M, weight average molecular weight 7800).

[0256] 4. Glass fiber fabric ((Y) component)

[0257] Glass fiber fabric (weight per unit area 600g / m 2 ), elongation at maximum load: 1.0%

[0258] For the glass fiber fabric, the elongation at the maximum load was measured by the following method.

[0259] A sample piece of glass fiber fabric of 250 mm × 25 mm was made. Using AUTOGRAPH "AG-10TA" (manufactured by Shimadzu Corporation), both ends of the sample were fixed with clamps. The test was carried out at a speed of 200 mm / min in the tensile mode. The displacement and load value were measured, and the elongation (strain) of the sample at the maximum load was calculated.

[0260] 5. Fiberglass mat

[0261] A vortex mat (weight per unit area 880 g / m2) made of continuous roving glass fiber (fiber diameter 23 μm) was used. 2 ) is a glass fiber mat obtained by needle punching.

[0262] Elongation at maximum load: 10%

[0263] The elongation at the maximum load of the glass fiber mat was measured by the following method.

[0264] A sample piece of glass fiber fabric of 250 mm × 25 mm was prepared and measured using AUTOGRAPH "AG-10TA" (manufactured by Shimadzu Corporation). Specifically, the two ends of the sample were fixed with a clamp, and the test was carried out at a speed of 200 mm / min in the tensile mode. The displacement and load value were measured, and the sample elongation (strain) at the maximum load was calculated.

[0265] Preparation Example 1 (Preparation of PP composition)

[0266] The above-mentioned component a, component b and component c were mixed in proportions of 68 mass %, 30 mass % and 2 mass %, respectively, and melt-kneaded (230° C.) to prepare pellets of a polypropylene resin composition (PP composition).

[0267] Comparative Preparation Example 1

[0268] In Preparation Example 1, pellets of a polypropylene-based resin composition (PP composition) were prepared in the same manner as in Preparation Example 1, except that the component b and the component c were not used.

[0269] Example 1

[0270] The pellets of the PP composition granulated in Preparation Example 1 were added to an extruder, melted, and extruded into a sheet to obtain an extruded sheet-like PP sheet 21 (see Figure 3 ). Glass fiber fabric 22 was laminated on both sides in a manner of sandwiching PP sheet 21 to produce a laminate. Further, PP sheet 21 was laminated on both sides in a manner of sandwiching the laminate to form the outermost layer. Then, while applying a pressure of 0.3 MPa using a laminator, heating and pressurizing at 230°C for 6 minutes were performed, and then the laminate was cooled and solidified, thereby obtaining a fiber-reinforced resin composite material (thickness; 1.5 mm) 10 (refer to Figure 3 ). A portion of the PP sheet 21 was impregnated with the glass fiber fabric 22 to obtain a fiber-reinforced resin composite material having an integrated layer. The weight ratio of the PP sheet 21 to the glass fiber fabric 22 was PP sheet:glass fiber fabric=1:1. The results obtained by the above-mentioned method are shown in Table 1.

[0271] Example 2

[0272] The pellets of the PP composition granulated in Preparation Example 1 are added to an extruder, and after melting, they are extruded into a sheet, thereby obtaining an extruded sheet-like PP sheet 21. The PP sheets 21 are laminated on both sides in a manner of sandwiching a glass fiber fabric 22 to prepare a laminate. Furthermore, both sides are laminated with a glass fiber fabric 22' in a manner of sandwiching the laminate. Finally, a PP sheet 21'' is laminated on the surface of the glass fiber fabric 22' on one side to make it the outermost layer. Next, while applying a pressure of 0.3 MPa using a laminator, heating and pressurizing are performed at 230°C for 6 minutes, and then the laminate is cooled and solidified, thereby obtaining a fiber-reinforced resin composite material (thickness; 1.5 mm) 10 (refer to Figure 4 ). A portion of the PP sheet was impregnated with glass mat fabric fibers to obtain a fiber-reinforced resin composite material having an integrated layer. The weight ratio of the PP sheet to the glass fiber fabric is PP sheet: glass fiber fabric = 1:2. The fiber-reinforced resin composite material was cut, and the cross section was polished to obtain a sample. The cross section of the sample was observed using a microscope "KH-8700" manufactured by HIROX Corporation (bright field, magnification: 50 times, 140 times). As a result, a layer (A) in which the weight of the thermoplastic resin composition (X) per unit area is relatively large relative to the weight of the inorganic fiber material (Y), and a layer (B) in which the weight of the thermoplastic resin composition (X) per unit area is relatively small relative to the weight of the inorganic fiber material (Y) is observed. It should be noted that in the microscope image of the above-mentioned sample cross section, for the glass fiber, its cross section is clearly observed in the form of a white or gray circle or oval. Therefore, by measuring the number of glass fibers observed in the cross section, layer (A) and layer (B) can be distinguished. The thickness ratio of layer (A) to layer (B) was 17 / 83. Table 1 shows the results of the evaluations conducted by the above methods.

[0273] Comparative Example 1

[0274] In Example 1, a fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that PP (Comparative Preparation Example 1) obtained by melting (230° C.) and granulating only the above-mentioned component a was used instead of the pellets of the PP composition granulated in Preparation Example 1. The results of the evaluation by the above method are shown in Table 1.

[0275] Comparative Example 2

[0276] In Comparative Example 1, a fiber-reinforced resin composite material was obtained in the same manner as in Comparative Example 1, except that the glass fiber weight and the resin weight ratio were changed as described in Table 1. Table 1 shows the results of the evaluations performed by the above methods.

[0277] Comparative Example 3

[0278] The pellets of the PP composition granulated in Preparation Example 1 were added to an extruder, and after melting, they were extruded into a sheet, and an extruded sheet-like PP sheet 21 was obtained. Glass fiber mats were laminated on both sides in a manner of sandwiching PP sheets 21 to prepare a laminate. Furthermore, PP sheets 21 were laminated on both sides in a manner of sandwiching the laminate to form the outermost layer. Then, while applying a pressure of 0.3 MPa using a laminator, heating and pressurizing at 230°C for 4 minutes were performed, and then it was cooled and solidified, thereby obtaining a fiber-reinforced resin composite material (thickness; 1.5 mm). A portion of the PP sheet 21 was impregnated with the glass fiber mat to obtain a fiber-reinforced resin composite material having an integrated layer. The weight ratio of PP sheet 21 to glass fiber mat was PP sheet: glass fiber mat = 65:35. The results obtained by the evaluation method described above are shown in Table 1.

[0279]

[0280] As shown in Example 1, the fiber-reinforced resin composite material of the present invention has excellent flame shielding properties, and can shield the flame even after 15 minutes, without burning and spreading to the back side. In addition, no penetration was also observed in the air jet test, confirming that the fiber-reinforced resin composite material of the present invention has high strength.

[0281] On the other hand, it can be seen that the sheet of Comparative Example 1 did not meet V-1 in the UL94 test and had poor flammability. In addition, for the sheet of Comparative Example 2, the flame penetrated to the back in 67 seconds. Since penetration occurred in the flame shielding test, the air jet test could not be evaluated.

[0282] Furthermore, as can be seen from the comparison between Example 2 and Comparative Example 3, the fiber-reinforced resin composite material of the present invention showed good results in the puncture test and the AUTOGRAPH test, and therefore, both the impact strength after heating and the penetration strength were high.

[0283] Industrial Applicability

[0284] It was confirmed that the fiber-reinforced resin composite material of the present invention exhibits high flame shielding properties, combustion resistance, and strength to withstand shock waves. Therefore, it is useful as a material for various industrial parts requiring high safety, such as aircraft, ships, automobile parts, electrical and electronic equipment parts, and building materials. In particular, it can be suitably used in various shells and frames of batteries that have traditionally used metals, contributing to the safety of automobiles, and it can be expected that the lightweighting will lead to improved energy efficiency, CO 2 Reduction of emissions, etc.

Claims

1. A fiber-reinforced resin composite material comprising a thermoplastic resin composition (X) and an inorganic fiber material (Y), The thermoplastic resin composition (X) comprises a thermoplastic resin and a phosphorus-based flame retardant, The phosphorus-based flame retardant comprises an intumescent flame retardant, The inorganic fiber material (Y) has an elongation of 5% or less at the maximum load.

2. The fiber-reinforced resin composite material according to claim 1, comprising at least one layer each of the following layer (A) and the following layer (B): a layer (A) in which the ratio of the weight of the thermoplastic resin composition (X) per unit area to the weight of the inorganic fiber material (Y) is relatively large, and The layer (B) has a relatively small ratio of the weight of the thermoplastic resin composition (X) to the weight of the inorganic fiber material (Y) per unit area.

3. The fiber-reinforced resin composite material according to claim 1, in, The total weight ratio of the thermoplastic resin composition (X) to the inorganic fiber material (Y) is 70 / 30 to 30 / 70.

4. The fiber-reinforced resin composite material according to claim 1, in, The total weight ratio of the thermoplastic resin composition (X) to the inorganic fiber material (Y) is 60 / 40 to 30 / 70.

5. The fiber-reinforced resin composite material according to claim 2, in, The thickness ratio of the layer (A) to the layer (B) is 1 / 99 to 50 / 50.

6. The fiber-reinforced resin composite material according to claim 1, in, The thermoplastic resin composition (X) further comprises a dispersant.

7. The fiber-reinforced resin composite material according to claim 6, in, The dispersant includes a copolymer of an α-olefin and an unsaturated carboxylic acid.

8. The fiber-reinforced resin composite material according to claim 6, in, The content of the dispersant is greater than 0 and less than 25 parts by mass based on 100 parts by mass of the phosphorus-based flame retardant.

9. The fiber-reinforced resin composite material according to claim 1, in, The inorganic fibers constituting the inorganic fiber material (Y) include at least one selected from the group consisting of glass fibers, ceramic fibers, metal fibers, and metal oxide fibers.

10. The fiber-reinforced resin composite material according to claim 1, in, The inorganic fiber material (Y) comprises an inorganic fiber fabric.

11. The fiber-reinforced resin composite material according to claim 1, in, The thermoplastic resin constituting the thermoplastic resin composition (X) includes a polypropylene-based resin, and the content of the polypropylene-based resin is 15 to 80% by mass based on the total weight.

12. The fiber-reinforced resin composite material according to claim 1, in, The content of the phosphorus-based flame retardant is 1 to 30% by mass relative to the total weight.

13. A molded body obtained by press-molding the fiber-reinforced resin composite material according to any one of claims 1 to 12.

14. A housing or a frame using the fiber-reinforced resin composite material according to any one of claims 1 to 12. 15 . A battery case using the fiber-reinforced resin composite material according to claim 1 .

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