Fiber-reinforced materials and structures.

Abstract

DEPCT63 The present invention reveals a fiber-reinforced material and... This difficult-to-break fiber-reinforced product (article) consists of groups of fibers. (fiber assembly)15 and matrix material12 are used to coat the fiber group15, in which the material Matrix 12 is a thermoplastic resin composition obtained by blending polyolefin resins. Polyamide resins and modified elastomers containing reactive groups. With podiamide resin, when the puncture test was performed at an impact speed of 1. meters / second or more, but at 4 meters / second or less, and when deflecting when subjected to force. The maximum impact force is defined as PM, and the maximum deflection at break is defined as PB and PB / PM. Greater than or equal to 4. Furthermore, when the amount of energy absorbed before reaching its maximum impact is... Defined as E1, the amount of energy absorbed after receiving maximum impact and before. The rupture event is defined as E2, and the total amount of energy absorbed by E1 and E2 is... It is defined as ET, and the ratio of E2 to ET is 70 percent or more. Made from this fiber-reinforced material. -----------------------------------------------------------

Description

Fiber-reinforced materials and structures

[0001] This invention relates to fiber-reinforced materials and structures. More specifically, it relates to fiber-reinforced materials and structures having excellent shock absorption capabilities.

[0002] Composite materials known as fiber-reinforced plastics have been known for some time. Generally, fiber-reinforced plastics are obtained by using a fiber aggregate, such as glass fiber nonwoven fabric, as a core material, coating this core material with a resin (matrix resin) which is a matrix material, and then curing it. In this case, thermosetting resins are often used as the matrix resin. Many of these resins have excellent fluidity in the uncured state and are selected from the viewpoint that they are easy to impregnate into the core material. However, thermosetting resins have the disadvantage of becoming brittle and prone to cracking once cured. For this reason, there is a need for fiber-reinforced materials and structures that are more resistant to cracking. From this viewpoint, it is conceivable to use a thermoplastic resin as the matrix resin. The following Patent Documents 1 to 3 are known as thermoplastic resins with excellent impact resistance.

[0003] Japanese Patent Publication No. 2013-147647, Japanese Patent Publication No. 2013-147646, Japanese Patent Publication No. 2013-147645

[0004] As mentioned above, when considering the use of a thermoplastic resin as the matrix resin, polyamide resins such as nylon 6 can be considered because they have excellent fluidity in the molten state and excellent flexibility and impact resistance in the solidified state. However, while polyamide resins can exhibit excellent impact resistance against relatively low-speed impacts, there is a problem in that it becomes difficult to maintain sufficient impact resistance as the speed of the input impact increases.

[0005] Furthermore, Patent Document 1 discloses a thermoplastic resin composition comprising a polyolefin resin, a polyamide resin, and a compatibilizer, having a phase separation structure comprising a continuous phase, a dispersed phase, and a finely dispersed phase further dispersed within the dispersed phase. This thermoplastic resin composition has been shown to exhibit excellent impact resistance. Patent Document 2 discloses that when PA11, PA610, PA614, PA1010 and / or PA10T are used as the polyamide resin and an acid-modified olefin-based thermoplastic elastomer is used as the compatibilizer, a thermoplastic resin composition obtained by melt-mixing the polyolefin resin, polyamide resin, and compatibilizer can exhibit excellent impact resistance. Furthermore, Patent Document 3 shows that a thermoplastic resin composition obtained by melt-mixing a mixed resin of polyamide resin and compatibilizer with a polyolefin resin exhibits excellent impact resistance. However, Patent Documents 1 to 3 do not consider applications to fiber-reinforced materials and structures.

[0006] This invention has been made in view of the above circumstances, and aims to provide fiber-reinforced materials and structures that are more resistant to cracking than conventional materials.

[0007] In other words, to solve the above problems, the present invention is as follows: The fiber-reinforced material according to claim 1 comprises fibers and a matrix material covering the fibers, wherein the matrix material is a thermoplastic resin composition comprising a polyolefin resin, a polyamide resin, and a modified elastomer having reactive groups for the polyamide resin. The fiber-reinforced material according to claim 2 is the fiber-reinforced material according to claim 1, wherein the fibers are a fiber aggregate. The fiber-reinforced material according to claim 3 is the fiber-reinforced material according to claim 1 or 2, wherein when a puncture test is performed at a striker speed of 1 m / s to 4 m / s, the displacement amount (mm) when the maximum impact force (N) is applied is P Ｍ The displacement (mm) at the fracture point is P Ｂ In that case, P Ｂ / P ＭIt is summarized that it is ≧4. The fiber reinforced material according to claim 4 is the fiber reinforced material according to claim 3, and further, the amount of energy (Nmm) absorbed until the maximum impact force (N) is applied is E １ is defined as, and the amount of energy (Nmm) absorbed from when the maximum impact force (N) is applied until reaching the breaking point is E ２ is defined as, and the energy amount E １ and the energy amount is E ２ is defined as the total absorbed energy amount (Nmm) of, and when E Ｔ is defined as, the ratio of E Ｔ to E ２ (E ２ / E Ｔ ) is summarized to be 70% or more. The fiber reinforced material according to claim 5 is the fiber reinforced material according to any one of claims 1 to 4, and it is summarized that the fiber aggregate is a woven or knitted fabric. The fiber reinforced material according to claim 6 is the fiber reinforced material according to any one of claims 1 to 4, and it is summarized that the fiber aggregate is a non-woven fabric. The fiber reinforced material according to claim 7 is the fiber reinforced material according to any one of claims 1 to 6, and the thermoplastic resin composition has a continuous phase (A) containing the polyolefin resin, and a dispersed phase (B) containing the polyamide resin dispersed in the continuous phase (A). The fiber reinforced material according to claim 8 is the fiber reinforced material according to claim 7, and the dispersed phase (B) further contains the modified elastomer, and the dispersed phase (B) has a continuous phase (B １ ) containing the polyamide resin, and a finely dispersed phase (B １ ) containing the modified elastomer dispersed in the continuous phase (B ２ ). The structure according to claim 9 is made of the fiber reinforced material according to any one of claims 1 to 8.

[0008] The fiber-reinforced material of the present invention makes it possible to create a fiber-reinforced material that is more resistant to cracking than conventional materials. In particular, it is possible to increase the energy expended on crack propagation before cracking occurs, and this action makes it possible to obtain a fiber-reinforced material that is more resistant to cracking. The structure of the present invention makes it possible to create a structure that is more resistant to cracking than conventional materials. In particular, it is possible to increase the energy expended on crack propagation before cracking occurs, and this action makes it possible to obtain a structure that is more resistant to cracking.

[0009] The present invention will be further described in the following detailed description with reference to the drawings, which refer to non-limiting examples of typical embodiments of the present invention, where similar reference numerals indicate similar parts in several of the drawings. This is a schematic diagram illustrating an example of the fiber-reinforced material and the structure. This is a schematic diagram illustrating another example of the fiber-reinforced material and the structure. This is a schematic diagram illustrating an example of the phase structure of the thermoplastic resin composition constituting the fiber-reinforced material and the structure. This is a schematic diagram illustrating another example of the phase structure of the thermoplastic resin composition constituting the fiber-reinforced material and the structure. This is a graph plotting the correlation between impact force and displacement obtained by subjecting test specimens of each example and comparative example to a puncture test (strike speed 1 m / sec). This is a graph plotting the correlation between impact force and displacement obtained by subjecting test specimens of each example and comparative example to a puncture test (strike speed 4 m / sec).

[0010] The matters presented herein are illustrative and illustrative to illustrate embodiments of the present invention, and are intended to provide what is considered to be the most effective and readily understandable explanation of the principles and conceptual features of the present invention. In this regard, it is not intended to show structural details of the present invention beyond what is necessary for a fundamental understanding of the invention, and it is intended that the description, in conjunction with the drawings, will make it clear to those skilled in the art how some forms of the present invention are actually embodied.

[0011] [1] Fiber-reinforced material The fiber-reinforced material (10) comprises fibers (15) and a matrix material (12) covering the fibers (15) (see Figures 1 and 2). The matrix material (12) is a thermoplastic resin composition obtained by blending a polyolefin resin, a polyamide resin, and a modified elastomer having reactive groups for the polyamide resin.

[0012] <1> Regarding the fibers, the fibers 15 are reinforcing materials within the fiber-reinforced material 10. These fibers 15 may be dispersed within the fiber-reinforced material 10 or aggregated. Generally, when the fiber length is short (i.e., when it is a short fiber), it is preferable that it be dispersed (see Figure 1). When the fiber length is long (i.e., when it is a long fiber), it is preferable that it be included as a fiber aggregate 15 (see Figure 2). That is, when the fiber 1 is a fiber aggregate 15, the fiber-reinforced material 10 comprises the fiber aggregate 15 and a matrix material 12 covering the fiber aggregate 15, wherein the matrix material 12 is a thermoplastic resin composition obtained by blending a polyolefin resin, a polyamide resin, and a modified elastomer having reactive groups for the polyamide resin.

[0013] When fiber 15 is a short fiber, it usually means that the fiber length is less than 15 mm. When it is a short fiber (including fiber filler), the fiber length is preferably 1 mm or more, more preferably 3 mm or more, and even more preferably 5 mm or more. On the other hand, when fiber 15 is a long fiber, the fiber length is preferably 15 mm or more. When the fiber length is 15 mm or more, when it is used to form a fiber aggregate, the constituent fibers (single fibers) that make up the fiber aggregate tend to intersect with one or more other constituent fibers, thereby increasing the tear strength of the fiber aggregate 15. From this viewpoint, when it is a long fiber, the fiber length is preferably 50 mm or more, more preferably 100 mm or more, and even more preferably 500 mm or more. When it is a long fiber, the maximum fiber length is not limited, but for example, a structure made of this fiber-reinforced material may include fibers that are continuous from one end to the other. In this case, the maximum fiber length is, for example, 1 × 10 ６ It can be less than or equal to mm.

[0014] When the fibers 15 are included as a fiber aggregate 15, the fiber aggregate 15 becomes the core material within the fiber-reinforced material 10. When the fibers 15 are a fiber aggregate 15, the aggregate form of the constituent fibers constituting the fiber aggregate 15 is not limited and includes woven fabrics, knitted fabrics, nonwoven fabrics (including fiber deposits, etc.). Only one of these may be used, or two or more may be used in combination. In this case, the weave form of the woven fabric, the knitting form of the knitted fabric, the accumulation form of the nonwoven fabric, etc., are not limited. The thickness of the fiber aggregate 15 is also not limited, but for example, 1 × 10 －３ The thickness can be between 100 mm and 150 mm. The basis weight of the fiber aggregate 15 is also not limited, but for example, 0.1 g / m². ２ More than 100000g / m ２ The following is possible:

[0015] The materials constituting the fibers 15 and the constituent fibers of the fiber aggregate 15 are not limited, and inorganic materials, organic materials, or a combination of these may be used. Examples of inorganic fibers include glass fibers, carbon fibers, activated carbon fibers, ceramic fibers (silicates, titanates, alumina, etc.), metal fibers, and boron fibers. These may be used individually or in combination of two or more. Examples of organic fibers include natural fibers and synthetic fibers. These may be used individually or in combination of two or more. Examples of natural fibers include plant fibers (kenaf fibers, etc.) and animal fibers (animal hair, silk, etc.). Examples of synthetic fibers include fibers formed from synthetic resins into a fiber shape. Examples of such synthetic resin fibers include polyamide resin fibers (aliphatic polyamides (such as nylon fibers), aromatic polyamides (aramid fibers, trade name "Kevlar," etc.)), polyester resin fibers (aliphatic polyesters, aromatic polyesters (such as polyethylene terephthalate fibers, polyethylene naphthalate fibers), etc.), polyolefin resin fibers (high molecular weight polyolefins (such as "Dyneema," trade name), etc.), and polybenzazole resin fibers (poly-paraphenylenebenzobisoxazole fibers (such as "Zylon," trade name), etc.). Other examples include vinylon fibers and polyarylate fibers. These can be used individually or in combination of two or more types.

[0016] Furthermore, the form of the fibers is not limited; they may be spun yarn, filament yarn, or a combination of both. Additionally, monofilaments may be used, multifilaments may be used, or a combination of both. The fibers 15 may also contain both short and long fibers. For example, a fiber-reinforced material containing both fiber aggregates 15 and fiber fillers can be used.

[0017] <2> Regarding the matrix material, the matrix material 12 is a material that covers the fibers 15, and in this fiber-reinforced material 10, it is a thermoplastic resin composition (see Figures 1 and 2). Also, the matrix material 12 is usually bound to the surface of the fibers 15. That is, the thermoplastic resin composition constituting the matrix material 12 is bound to the fibers 15. In particular, when the fibers 15 are a fiber aggregate 15, the thermoplastic resin composition constituting the matrix material 12 is bound to the constituent fibers constituting the fiber aggregate 15, and the matrix material 12 is usually impregnated into the interior of the fiber aggregate 15. That is, when the fibers 15 are a fiber aggregate 15, the matrix material 12 constituting the surface side of the fiber aggregate 15 and the matrix material 12 constituting the back side of the fiber aggregate 15 are integrally fused within the fiber aggregate 15 (see Figure 2). In other words, the fiber aggregate 15 is embedded in the matrix material 12. Furthermore, the matrix material 12 is a thermoplastic resin composition comprising a polyolefin resin, a polyamide resin, and a modified elastomer having reactive groups for the polyamide resin.

[0018] (1) Polyolefin resins Polyolefin resins are homopolymers of olefins and / or copolymers of olefins. The olefins constituting the polyolefin resin are not particularly limited, but examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. These may be used individually or in combination of two or more. That is, examples of polyolefin resins include polyethylene resin, polypropylene resin, poly-1-butene, poly-1-hexene, poly-4-methyl-1-pentene, etc. These polymers may be used individually or in combination of two or more. That is, the polyolefin resin may be a mixture of the above polymers.

[0019] Examples of the polyethylene resins mentioned above include ethylene homopolymers and copolymers of ethylene with other olefins. Examples of the latter include ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, and ethylene-4-methyl-1-pentene copolymers (where at least 50% of the total constituent units are derived from ethylene).

[0020] Polypropylene resins include propylene homopolymers and copolymers of propylene and other olefins. On the other hand, the other olefins that constitute the copolymer of propylene and other olefins include the various olefins mentioned above (except propylene). Among these, ethylene and 1-butene are preferred. That is, propylene-ethylene copolymers and propylene-1-butene copolymers are preferred. Furthermore, the copolymer of propylene and other olefins may be a random copolymer or a block copolymer. In addition, in the copolymer of propylene and other olefins, 50% or more of the total number of constituent units are derived from propylene.

[0021] In thermoplastic resin compositions, the polyolefin resin preferably contains a homopolymer, and more preferably the homopolymer is the main component (usually 70% by mass or more of the total, but may be 100% by mass). That is, it is preferable that the polyolefin resin is a homopolymer or a mixture thereof, with one of the olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene as the monomer. Among these, it is particularly preferable that the polyolefin resin contains a propylene homopolymer, and more preferably the propylene homopolymer is the main component (usually 70% by mass or more of the total, but may be 100% by mass). Furthermore, when the polyolefin resin is mainly composed of a homopolymer and the propylene homopolymer is the main component, other homopolymers besides propylene homopolymer include ethylene homopolymer and / or 1-butene homopolymer.

[0022] Furthermore, polyolefin resins are polyolefins that do not have affinity for polyamide resins and do not possess reactive groups that can react with polyamide resins. In this respect, they differ from modified elastomers.

[0023] In thermoplastic resin compositions, the average molecular weight (weight-average molecular weight) of the polyolefin resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 100,000 to 450,000, and particularly preferably 200,000 to 400,000. This weight-average molecular weight is the weight-average molecular weight on a polystyrene basis calculated by gel permeation chromatography (GPC). Furthermore, in the present invention, when a homopolymer is used as the polyolefin resin, each of the above-mentioned numerical ranges for weight-average molecular weight can be reinterpreted as the numerical range for number-average molecular weight.

[0024] (2) Polyamide resins Polyamide resins are polymers having a chain-like skeleton formed by the polymerization of multiple monomers via amide bonds (-NH-CO-). Examples of monomers constituting polyamide resins include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid, and lactams such as ε-caprolactam, undecanolactam, and ω-lauryllactam. These may be used individually or in combination of two or more.

[0025] Furthermore, polyamide resins can also be obtained by copolymerization of diamines and dicarboxylic acids. In this case, the diamine monomers include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, and 1,16-diaminohexadecane. Examples include aliphatic diamines such as n, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane; alicyclic diamines such as cyclohexanediamine and bis-(4-aminocyclohexyl)methane; and aromatic diamines such as xylylenediamine (p-phenylenediamine and m-phenylenediamine, etc.). These may be used individually or in combination of two or more.

[0026] Furthermore, examples of dicarboxylic acids as monomers include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, and octadecanediic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. These may be used individually or in combination of two or more.

[0027] Specifically, examples of polyamide resins include polyamide 6, polyamide 66, polyamide 11, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, polyamide 9T / 2M-8T, etc. These polyamides may be used individually or in combination of two or more.

[0028] Furthermore, in the present invention, plant-derived polyamide resins can be used among the various polyamide resins described above. Plant-derived polyamide resins are desirable from the viewpoint of environmental protection (especially from the viewpoint of carbon neutrality) because they are resins that use monomers obtained from plant-derived components such as vegetable oils. Examples of plant-derived polyamide resins include polyamide 11 (hereinafter also simply referred to as "PA11"), polyamide 610 (hereinafter also simply referred to as "PA610"), polyamide 612 (hereinafter also simply referred to as "PA612"), polyamide 614 (hereinafter also simply referred to as "PA614"), polyamide 1010 (hereinafter also simply referred to as "PA1010"), polyamide 1012 (hereinafter also simply referred to as "PA1012"), polyamide 10T (hereinafter also simply referred to as "PA10T"), etc. These may be used individually or in combination of two or more.

[0029] Of the above, PA11 has a structure in which monomers having 11 carbon atoms are linked via amide bonds. For PA11, aminoundecanoic acid derived from castor oil can be used as the monomer. It is preferable that the constituent units derived from monomers having 11 carbon atoms account for 50% or more of the total constituent units in PA11, and may be 100%. PA610 has a structure in which monomers having 6 carbon atoms and monomers having 10 carbon atoms are linked via amide bonds. For PA610, sebacic acid derived from castor oil can be used as the monomer. It is preferable that the sum of constituent units derived from monomers having 6 carbon atoms and constituent units derived from monomers having 10 carbon atoms in PA610 accounts for 50% or more of the total constituent units, and may be 100%. PA1010 has a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are copolymerized. PA1010 can use 1,10-decanediamine (decamethylenediamine) and sebacic acid, both derived from castor oil, as monomers. Preferably, the total amount of constituent units derived from these 10-carbon diamines and 10-carbon dicarboxylic acids in PA1010 is 50% or more of the total constituent units, and may be 100%.

[0030] PA614 has a structure in which a monomer having 6 carbon atoms and a monomer having 14 carbon atoms are linked via an amide bond. In PA614, a plant-derived dicarboxylic acid having 14 carbon atoms can be used as the monomer. Preferably, the total of the constituent units derived from the monomer having 6 carbon atoms and the constituent units derived from the monomer having 14 carbon atoms in PA614 is 50% or more of the total constituent units, and may be 100%. PA10T has a structure in which a diamine having 10 carbon atoms and terephthalic acid are linked via an amide bond. In PA10T, 1,10-decanediamine (decamethylenediamine) derived from castor oil can be used as the monomer. Preferably, the total of the constituent units derived from the diamine having 10 carbon atoms and the constituent units derived from terephthalic acid in PA10T is 50% or more of the total constituent units, and may be 100%.

[0031] Among the five types of plant-derived polyamide resins mentioned above, PA11 is superior to the other four types of plant-derived polyamide resins in terms of low water absorption, low specific gravity, and high degree of plant-derivedness. Polyamide 610 is inferior to PA11 in terms of water absorption rate, chemical resistance, and impact strength, but is superior in terms of heat resistance (melting point) and rigidity (strength). Furthermore, it has lower water absorption and better dimensional stability than polyamide 6 and polyamide 66, so it can be used as a substitute material for polyamide 6 and polyamide 66. Polyamide 1010 is superior to PA11 in terms of heat resistance and rigidity. Furthermore, its degree of plant-derivedness is equivalent to PA11, so it can be used in parts that require greater durability. Polyamide 10T contains aromatic rings in its molecular backbone, so it has a higher melting point and higher rigidity than polyamide 1010. Therefore, it can be used in harsh environments (heat-resistant parts, parts that require high strength).

[0032] The weight-average molecular weight of the polyamide resin is not particularly limited, but for example, it can be 5,000 to 100,000, preferably 7,500 to 50,000, and more preferably 10,000 to 50,000. The weight-average molecular weight of the polyamide resin is the weight-average molecular weight on a polystyrene basis determined by gel permeation chromatography (GPC).

[0033] (3) Modified elastomer The modified elastomer is an elastomer having reactive groups for polyamide resins. Preferably, this modified elastomer exhibits affinity for polyamide resins using the above-mentioned reactive groups, and at the same time, also exhibits affinity for polyolefin resins. That is, it is preferable that the modified elastomer has reactive groups for polyamide resins and is a compatibilizer that is compatible with both polyolefin resins and polyamide resins. The modified elastomer may be included in the thermoplastic resin composition as an unreacted modified elastomer, as a reaction product with the polyamide resin, or in both of these forms.

[0034] The reactive groups mentioned above include acid anhydride groups (-CO-O-OC-), carboxyl groups (-COOH), and epoxy groups {-C}. ２ O (a three-membered ring structure consisting of two carbon atoms and one oxygen atom), oxazoline group (-C ３ H ４Examples include NO and isocyanate groups (-NCO). These may be used individually or in combination of two or more. These reactive groups can be introduced into the elastomer before modification (unmodified elastomer) by modification. Specifically, examples include acid-modified elastomers, epoxy-modified elastomers, and oxazoline-modified elastomers. Among these, acid-modified elastomers are preferred, and more preferably, they are modified elastomers with acid anhydrides or carboxylic acids. It is particularly preferable that the modified elastomer has an acid anhydride group or a carboxyl group in the side chain or terminal of the molecule. The amount of acid modification is not particularly limited; for example, the number of acid anhydride groups or carboxyl groups contained in one molecule of modified elastomer is preferably 1 or more, more preferably 2 to 50, even more preferably 3 to 30, and particularly preferably 5 to 20. The above modified elastomers can be used alone or in combination of two or more.

[0035] Examples of elastomers before modification include olefin-based elastomers and styrene-based elastomers. From the viewpoint of compatibility with polyolefin resin, olefin-based elastomers are particularly preferred. The olefin-based elastomer is preferably an α-olefin copolymer containing structural units derived from α-olefins having 3 to 8 carbon atoms, and can be an ethylene-α-olefin copolymer, an α-olefin copolymer, an α-olefin-non-conjugated diene copolymer, or an ethylene-α-olefin-non-conjugated diene copolymer. Of these, ethylene-α-olefin copolymer, α-olefin copolymer, and ethylene-α-olefin-non-conjugated diene copolymer are particularly preferred.

[0036] Examples of non-conjugated dienes include linear acyclic dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, and 1,6-hexadiene; and branched acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, and dihydromyrcene. Compounds include alicyclic diene compounds such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo[2.2.1]-hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene.

[0037] Specific examples of olefin elastomers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-pentene copolymer, propylene-1-hexene copolymer, and propylene-1-octene copolymer. Of these, ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene copolymer are preferred.

[0038] Furthermore, examples of the above-mentioned styrene-based elastomers (i.e., styrene-based thermoplastic elastomers having a styrene skeleton) include block copolymers of aromatic vinyl compounds and conjugated diene compounds, and their hydrogenated products. Examples of the above-mentioned aromatic vinyl compounds include alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-tert-butylstyrene; p-methoxystyrene and vinylnaphthalene. Examples of the above-mentioned conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadiene.

[0039] Specific examples of styrene-based elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene / butylene-styrene copolymer (SEBS), and styrene-ethylene / propylene-styrene copolymer (SEPS).

[0040] Examples of acid anhydrides for acid denaturation include maleic anhydride, phthalic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and butenyl succinic anhydride. Of these, maleic anhydride, phthalic anhydride, and itaconic anhydride are preferred. Examples of carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

[0041] Among the various modified elastomers mentioned above, acid anhydride-modified elastomers are preferred as the modified elastomer in the thermoplastic resin composition, and maleic anhydride-modified elastomers are particularly preferred. Furthermore, acid-modified α-olefin copolymers containing structural units derived from α-olefins having 3 to 8 carbon atoms are preferred. Specifically, olefin-based thermoplastic elastomers with a copolymer of ethylene or propylene and α-olefins having 3 to 8 carbon atoms as the backbone are preferred, and more specifically, elastomers modified with maleic anhydride, such as maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene-1-butene copolymer, maleic anhydride-modified ethylene-1-hexene copolymer, and maleic anhydride-modified ethylene-1-octene copolymer, are preferred. Specifically, α-olefin copolymers such as the "Tafmer series" (trade name) from Mitsui Chemicals, Inc. and the "AMPLIFY series" (trade name) from Dow Chemical can be used.

[0042] The weight-average molecular weight of the modified elastomer in the thermoplastic resin composition is not particularly limited, but for example, it can be 10,000 to 500,000, preferably 20,000 to 500,000, and more preferably 30,000 to 300,000. The weight-average molecular weight of the modified elastomer is the weight-average molecular weight on a polystyrene basis determined by gel permeation chromatography (GPC).

[0043] (4) Other components The thermoplastic resin composition may not contain any thermoplastic resins other than the polyolefin resin, polyamide resin, and modified elastomer mentioned above, and may consist only of the thermoplastic resins mentioned above, but may also contain other components. These may be used individually or in combination of two or more. Other components include other thermoplastic resins. Specifically, examples include polyester resins (polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polybutylene succinate, polyethylene succinate, polylactic acid), etc. These may be used individually or in combination of two or more. When other thermoplastic resins are included, it is preferable that the other thermoplastic resin is 25% by mass or less (further 20% by mass or less, further 15% by mass or less, further 10% by mass or less, further 5% by mass or less, and 1% by mass or more) when the total of the polyolefin resin, polyamide resin, modified elastomer, and other thermoplastic resins is 100% by mass.

[0044] Other additives that can be incorporated include nucleating agents, antioxidants, heat stabilizers, weathering agents, light stabilizers, plasticizers, UV absorbers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, anti-foaming agents, weld strength improvers, natural oils, synthetic oils, waxes, etc. These may be used individually or in combination of two or more.

[0045] Examples of the nucleating agents and reinforcing fillers mentioned above include silicates such as talc, silica, clay, montmorillonite, and kaolin; carbonates such as calcium carbonate, lithium carbonate, and magnesium carbonate; metal oxides such as alumina, titanium oxide, and zinc oxide; metals such as aluminum, iron, silver, and copper; hydroxides such as aluminum hydroxide and magnesium hydroxide; sulfides such as barium sulfate; carbides such as charcoal and bamboo charcoal; titanides such as potassium titanate and barium titanate; celluloses such as cellulose microfibrils and cellulose acetate; and carbons such as fullerenes.

[0046] Examples of antioxidants include phenolic compounds, organic phosphite compounds, and thioether compounds. Examples of heat stabilizers include hindered amine compounds. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and benzoate compounds. Examples of antistatic agents include nonionic compounds, cationic compounds, and anionic compounds. Examples of flame retardants include halogen compounds, phosphorus compounds (nitrogen-containing phosphate compounds, phosphate esters, etc.), nitrogen compounds (guanidine, triazine, melamine, or derivatives thereof, etc.), inorganic compounds (metal hydroxides, etc.), boron compounds, silicone compounds, sulfur compounds, and red phosphorus compounds. Examples of flame retardant additives include antimony compounds, zinc compounds, bismuth compounds, magnesium hydroxide, and clayey silicates.

[0047] <3> Phase Structure The thermoplastic resin composition is made by blending a polyolefin resin, a polyamide resin, and a modified elastomer. The thermoplastic resin composition may exhibit any phase structure, and its phase structure is not particularly limited, but for example, it can take the following phase structures (1) to (3). That is, Phase structure (1): A phase structure having a continuous phase (A) containing a polyolefin resin and a dispersed phase (B) containing a polyamide resin dispersed in the continuous phase (A) (see Figure 3). However, other phase structures having a continuous phase containing a polyamide resin and a dispersed phase dispersed in this continuous phase cannot coexist. Phase structure (2): A phase structure having a continuous phase containing a polyamide resin and a dispersed phase containing a polyolefin resin dispersed in this continuous phase. However, other phase structures having a continuous phase containing a polyolefin resin and a dispersed phase dispersed in this continuous phase cannot coexist. Phase structure (3): A continuous phase (A) containing a polyolefin resin １ ) and continuous phase (A １ A dispersed phase containing polyamide resin (B) dispersed in ) Ａ１ ) and a continuous phase containing polyamide resin (A ２ ) and continuous phase (A ２ A dispersed phase containing a modified elastomer (B) dispersed in ) Ａ２ A phase structure having (see Figure 4). Among these phase structures, it is preferable to exhibit the above-described phase structure (1) or phase structure (3).

[0048] More specifically, phase structure (1) can have a continuous phase (A) containing a polyolefin resin and a dispersed phase (B) dispersed within this continuous phase (A), which contains a polyamide resin. This dispersed phase (B) may contain a modified elastomer in addition to the polyamide resin. １ ) and this continuous phase (B １ A finely dispersed phase dispersed within ) and a finely dispersed phase (B) containing a modified elastomer ２ ) and can have (see Figure 3). In this case, the phase structure (1) has a further microdispersive phase (B) within the dispersed phase (B). １This results in a multiphase structure having ). Phase structure (1) is a phase structure that does not have any continuous phases other than continuous phase (A). Furthermore, in phase structure (1), the modified elastomer may be an unreacted modified elastomer, a reaction product with a polyamide resin, or a mixture thereof.

[0049] On the other hand, to describe the phase structure (3) in more detail, the phase structure (3) is a continuous phase (A) containing polyolefin resin. １ ) and this continuous phase (A １ A dispersed phase dispersed within ) and comprising a polyamide resin (B Ａ１ ) and can have this dispersed phase (B Ａ１ ) may include modified elastomers in addition to polyamide resins. Furthermore, phase structure (3) is continuous phase (A １ ) and dispersed phase (B Ａ１ ) along with a continuous phase containing polyamide resin (A ２ ) and this continuous phase (A ２ A dispersed phase dispersed within ) and comprising a modified elastomer (B Ａ２ ) and can have (see Figure 4). That is, the phase structure (3) is a continuous phase (A １ ) and continuous phase (A ２ It can exhibit a co-continuous phase structure in which two continuous phases (B) coexist. Ａ１ ) is this dispersed phase (B Ａ１ ) a continuous phase within which a continuous phase containing polyamide resin (B Ａ１１ ) and this continuous phase (B Ａ１１ A finely dispersed phase dispersed within ) and a finely dispersed phase (B) containing a modified elastomer Ａ１２ ) and can have. In this case, the phase structure (3) is the dispersed phase (B Ａ１ ) contains a further finely dispersed phase (B Ａ１２ The result is a multiphase structure having ). Furthermore, the phase structure (3) is a continuous phase (A １ ) and continuous phase (A ２The phase structure has no continuous phases other than the one shown. Furthermore, in phase structure (3), the modified elastomer may be an unreacted modified elastomer, a reaction product with a polyamide resin, or a mixture thereof.

[0050] In the case of the above phase structure (1), the continuous phase (A) contains a polyolefin resin. The polyolefin resin is preferably the main component of the continuous phase (A) (usually 70% by mass or more, and may be 100% by mass, relative to the entire continuous phase A). Furthermore, the dispersed phase (B) contains a polyamide resin and may further contain a modified elastomer. The polyamide resin (or, if the dispersed phase (B) contains a modified elastomer, the polyamide resin and the modified elastomer) is preferably the main component of the dispersed phase (B) (usually 70% by mass or more, and may be 100% by mass, relative to the entire dispersed phase B). Furthermore, the dispersed phase (B) contains the continuous phase (B １ ) and this continuous phase (B １ (B) A finely dispersed phase dispersed within ２ ) and can have. Of these, continuous phase (B １ ) contains polyamide resin. The polyamide resin is the continuous phase (B １ ) Main component (continuous phase B １ It is preferable that the total amount is usually 70% by mass or more, and may be 100% by mass. Also, a finely dispersed phase (B ２ ) contains a modified elastomer. The modified elastomer is a finely dispersed phase (B ２ ) Main component (finely dispersed phase B ２ It is preferable that the amount is usually 70% by mass or more of the total, and may be 100% by mass.

[0051] In the case of the above phase structure (3), the continuous phase (A １ ) contains polyolefin resin. The polyolefin resin is the continuous phase (A １ ) Main component (continuous phase A １ It is preferable that the total amount is usually 70% by mass or more, and may be 100% by mass. Also, the continuous phase (A １ Dispersed phase (B) relative to ) Ａ１) comprises a polyamide resin and may further contain a modified elastomer. The polyamide resin (if the dispersed phase (B) contains a modified elastomer, then the polyamide resin and the modified elastomer) comprises the dispersed phase (B Ａ１ ) Main component (dispersed phase B Ａ１ It is preferable that the amount is usually 70% by mass or more of the total, and may be 100% by mass. Furthermore, the dispersed phase (B Ａ１ ) is this dispersed phase (B Ａ１ ) Continuous phase (B Ａ１１ ) and this continuous phase (B Ａ１１ (B) A finely dispersed phase dispersed within Ａ１２ ) and (may not have) have (but may have). When this multiphase structure is present, the continuous phase (B Ａ１１ ) contains polyamide resin. The polyamide resin is the continuous phase (B Ａ１１ ) Main component (continuous phase B Ａ１１ It is preferable that the total amount is usually 70% by mass or more, and may be 100% by mass. Also, a finely dispersed phase (B Ａ１２ ) contains a modified elastomer. The modified elastomer is a finely dispersed phase (B Ａ１２ ) Main component (finely dispersed phase B Ａ１２ It is preferable that the total amount is usually 70% by mass or more, and may be 100% by mass. Also, the continuous phase (A ２ ) contains polyamide resin. The polyamide resin is a continuous phase (A ２ ) Main component (continuous phase A ２ It is preferable that the total amount is usually 70% by mass or more, and may be 100% by mass. Also, the continuous phase (A ２ Dispersed phase (B) relative to ) Ａ２ ) contains a modified elastomer. The modified elastomer is dispersed in the (B) phase. Ａ２ ) Main component (dispersed phase B Ａ２ It is preferable that the amount is usually 70% by mass or more of the total, and may be 100% by mass.

[0052] When having such a phase structure (1) or phase structure (3), the fiber reinforced material can exhibit more excellent impact absorption ability. As will be described later, this phase structure can be obtained by melt-kneading a melt-kneaded product of a polyamide resin and a modified elastomer and a polyolefin resin. Incidentally, in the thermoplastic resin composition of the fiber reinforced material, the polyamide resin and the modified elastomer may be reacted. That is, it may be a reaction product (reaction product of a polyamide resin and a modified elastomer) in which a reactive group possessed by the modified elastomer is reacted with the polyamide resin. For example, in the phase structure (1), at the interface between the continuous phase (A) and the dispersed phase (B), and / or, the continuous phase (B １ ), and the interface between the finely dispersed phase (B ２ ), the above-mentioned reaction product may be present. Similarly, in the phase structure (3), at the interface between the continuous phase (A １ ), and the continuous phase (A ２ ), the interface between the continuous phase (A １ ), and the dispersed phase (B Ａ１ ), the interface between the continuous phase (B Ａ１１ ), and the finely dispersed phase (B Ａ１２ ), etc., the above-mentioned reaction product may be present.

[0053] Various phase structures can be observed with a field emission scanning electron microscope (FE-SEM) on the treated surface of a test piece (test piece of the thermoplastic resin composition) that has been subjected to an oxygen plasma etching treatment and then further subjected to an osmium coating treatment. In particular, the dispersed phase and the finely dispersed phase can be observed with an image magnified 1000 times or more (usually 10,000 times or less) in this method. Also, the components constituting each phase can be specified by performing energy dispersive X-ray analysis (EDS) during observation using a field emission scanning electron microscope (FE-SEM).

[0054] The dispersed phase of the thermoplastic resin composition (dispersed phase B in FIG. 3, dispersed phase B in FIG. 4 Ａ１The size of () is not particularly limited, but its dispersion diameter (average dispersion diameter) is preferably 10,000 nm or less, more preferably 50 nm or more and 8,000 nm or less, and still more preferably 100 nm or more and 4,000 nm or less. The dispersion diameter of this dispersed phase can be measured in an enlarged image of 1,000 times or more obtained using an electron microscope. That is, the longest diameter of each of 20 dispersed phases randomly selected from a predetermined region in the image is measured, and the average value of the obtained longest diameters is taken as the first average value. Then, the further average value of the first average values measured in five different regions in the image is the average dispersion diameter (long-axis average dispersion diameter) of the dispersed phase.

[0055] The dispersed phase of the thermoplastic resin composition (dispersed phase B in FIG. 3, dispersed phase B in FIG. 4 Ａ１ ) The fine dispersed phase contained therein (fine dispersed phase B in FIG. 3 ２ , fine dispersed phase B in FIG. 4 Ａ１２ ) The size of is not particularly limited, but its dispersion diameter (average dispersion diameter) is preferably 5 nm or more and 1,000 nm or less, more preferably 5 nm or more and 600 nm or less, still more preferably 10 nm or more and 400 nm or less, and particularly preferably 15 nm or more and 350 nm or less. The dispersion diameter of this fine dispersed phase can be measured in an enlarged image of 1,000 times or more obtained using an electron microscope. That is, the longest diameter of each of 20 fine dispersed phases randomly selected from a predetermined region in the image is measured, and the average value of the obtained longest diameters is taken as the first average value. Then, the further average value of the first average values measured in five different regions in the image is the average dispersion diameter (long-axis average dispersion diameter) of the fine dispersed phase.

[0056] <4> Regarding the formulation, in a thermoplastic resin composition, when the total of polyolefin resin, polyamide resin, and modified elastomer is 100% by mass, the proportion of polyolefin resin can be 2% by mass or more and 90% by mass or less. This proportion is preferably 5% by mass or more and 85% by mass or less, more preferably 10% by mass or more and 83% by mass or less, more preferably 15% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 78% by mass or less, more preferably 25% by mass or more and 75% by mass or less, more preferably 30% by mass or more and 73% by mass or less, and more preferably 35% by mass or more and 70% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made of this fiber-reinforced material can be obtained.

[0057] In a thermoplastic resin composition, when the total of polyolefin resin, polyamide resin, and modified elastomer is 100% by mass, the proportion of polyamide resin and modified elastomer (some or all of these may be reacted with each other; the same applies hereinafter) can be 10% by mass or more and 98% by mass or less. This proportion is preferably 15% by mass or more and 95% by mass or less, more preferably 17% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, more preferably 22% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 75% by mass or less, more preferably 27% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 65% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made of this fiber-reinforced material can be obtained.

[0058] In a thermoplastic resin composition, when the total of polyolefin resin, polyamide resin, and modified elastomer is 100% by mass, the proportion of polyamide resin can be 1% by mass or more and 75% by mass or less. This proportion is preferably 15% by mass or more and 72% by mass or less, more preferably 20% by mass or more and 70% by mass or less, more preferably 22% by mass or more and 68% by mass or less, more preferably 25% by mass or more and 65% by mass or less, more preferably 27% by mass or more and 57% by mass or less, more preferably 29% by mass or more and 53% by mass or less, and more preferably 33% by mass or more and 49% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made from this fiber-reinforced material can be obtained.

[0059] In a thermoplastic resin composition, when the total of polyolefin resin, polyamide resin, and modified elastomer is 100% by mass, the proportion of modified elastomer can be 1% by mass or more and 60% by mass or less. Preferably, this proportion is 5% by mass or more and 53% by mass or less, more preferably 11% by mass or more and 45% by mass or less, more preferably 12% by mass or more and 40% by mass or less, more preferably 13% by mass or more and 38% by mass or less, more preferably 14% by mass or more and 36% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and more preferably 18% by mass or more and 34% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made from this fiber-reinforced material can be obtained.

[0060] Furthermore, in a thermoplastic resin composition, if the total of polyolefin resin and polyamide resin is 100% by mass, the proportion of polyamide resin can be 1.5% by mass or more and 88% by mass or less. This proportion is preferably 3% by mass or more and 75% by mass or less, more preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 65% by mass or less, more preferably 15% by mass or more and 60% by mass or less, more preferably 18% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and more preferably 25% by mass or more and 45% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made from this fiber-reinforced material can be obtained.

[0061] Furthermore, in a thermoplastic resin composition, when the total of the polyamide resin and the modified elastomer is 100% by mass, the proportion of the modified elastomer can be 20% by mass or more and 90% by mass or less. Preferably, this proportion is 22% by mass or more and 88% by mass or less, more preferably 25% by mass or more and 86% by mass or less, more preferably 27% by mass or more and 75% by mass or less, more preferably 29% by mass or more and 70% by mass or less, more preferably 32% by mass or more and 66% by mass or less, and more preferably 36% by mass or more and 60% by mass or less. Within the above range, a fiber-reinforced material with excellent shock absorption properties and a structure made of this fiber-reinforced material can be obtained.

[0062] Furthermore, when the total of the aforementioned polyolefin resin, polyamide resin, and modified elastomer is set to 100% by mass, the proportion of polyolefin resin is usually equal to the proportion of continuous phase (A) when the entire phase is set to 100% by mass, in the case of phase structure (1) (see Figure 3) described above. On the other hand, in the case of phase structure (3) (see Figure 4), the proportion of continuous phase (A) when the entire phase is set to 100% by mass is usually equal to the proportion of continuous phase (A) when the entire phase is set to 100% by mass. １ This is equal to the ratio of volume. Here, the ratio is a volume ratio, but it is usually equal to the area ratio to which this volume ratio is reflected (the same applies hereafter).

[0063] When the total of the aforementioned polyolefin resin, polyamide resin, and modified elastomer is taken as 100% by mass, the proportions of the polyamide resin and modified elastomer are usually equal to the proportion of the dispersed phase (B) when the entire phase is taken as 100% by mass, in the case of the aforementioned phase structure (1) (see Figure 3). On the other hand, in the case of phase structure (3) (see Figure 4), the proportions of the dispersed phase (B) are usually equal to the proportion of the dispersed phase (B) when the entire phase is taken as 100% by mass. Ａ１ ) and continuous phase (A ２ ) and dispersed phase (B Ａ２ It is equal to the sum of the two.

[0064] When the total of the aforementioned polyolefin resin, polyamide resin, and modified elastomer is set to 100% by mass, the proportion of polyamide resin is, in the case of the aforementioned phase structure (1) (see Figure 3), the proportion of the continuous phase (B) when the entire phase is set to 100% by mass. １) is equal to the ratio of ). On the other hand, in the case of phase structure (3) (see Figure 4), the continuous phase (A) is usually equal to the ratio of the entire phase when the entire phase is considered to be 100% by mass. ２ ) and continuous phase within the dispersed phase (B Ａ１１ It is equal to the sum of the two.

[0065] When the total of the polyolefin resin, polyamide resin, and modified elastomer mentioned above is set to 100% by mass, the proportion of the modified elastomer is, in the case of the phase structure (1) mentioned above (see Figure 3), usually the proportion of the finely dispersed phase (B) when the entire phase is set to 100% by mass. ２ ) is equal to the proportion of ). On the other hand, in the case of phase structure (3) (see Figure 4), the finely dispersed phase (B) is usually equal to the proportion of the entire phase when the entire phase is considered to be 100% by mass. Ａ１２ ) and dispersed phase (B Ａ２ It is equal to the sum of the two.

[0066] When the total of the polyolefin resin and polyamide resin mentioned above is set to 100% by mass, the proportion of polyamide resin is, in the case of the phase structure (1) mentioned above (see Figure 3), usually the proportion of the continuous phase (B) when the entire phase is set to 100% by mass. １ ) is equal to the ratio of ). On the other hand, in the case of phase structure (3) (see Figure 4), the continuous phase (A) is usually equal to the ratio of the entire phase when the entire phase is considered to be 100% by mass. ２ ) and the finely dispersed phase (B Ａ１２ Dispersed phase (B) that does not have Ａ１ ) and the finely dispersed phase (B Ａ１２ Dispersed phase (B) having ) Ａ１ ) Among the dispersed phase continuous phase (B Ａ１１ It is equal to the sum of the two.

[0067] When the total of the polyamide resin and modified elastomer mentioned above is set to 100% by mass, the proportion of the modified elastomer is, in the case of the phase structure (1) mentioned above (see Figure 3), usually the proportion of the finely dispersed phase (B) when the entire phase is set to 100% by mass. ２ ) is equal to the proportion of ). On the other hand, in the case of phase structure (3) (see Figure 4), the dispersed phase (B) is usually equal to the proportion of the entire phase when the entire phase is considered to be 100% by mass. Ａ２ ) and the finely dispersed phase (B Ａ１２ It is equal to the sum of the two.

[0068] <5> Regarding impact absorption characteristics, the fiber-reinforced material of the present invention and the structure described later can exhibit excellent impact absorption characteristics. Specifically, when a puncture test is performed at a striker speed of 1 m / s to 4 m / s, the displacement (mm) when the maximum impact force (N) is applied is P Ｍ Let P be the displacement (mm) at the fracture point. Ｂ In that case, P Ｂ / P Ｍ ≧4 (usually P Ｂ / P Ｍ It can be said that ≤ 10. That is, the displacement from the time a crack occurs until fracture occurs is more than four times greater than the displacement from the time a crack occurs due to the impact input. Therefore, in addition to the energy that can be absorbed before crack formation, a large amount of energy can also be absorbed during crack propagation, so the total amount of energy absorbed until fracture can be increased, and a better shock absorption capacity can be achieved. In other words, this fiber-reinforced material and this structure can be said to be a material that is less prone to cracking. Generally, although a material can absorb shock by cracking, the shock absorption capacity decreases rapidly after cracking, so the total amount of absorbed energy is designed to be as large as the amount of energy that can be absorbed before crack formation. To achieve this, it is necessary to shift the design in the direction of increasing length, size and weight, such as by increasing the thickness, but with this fiber-reinforced material and this structure, the total amount of absorbed energy can be increased while being designed to be thinner, lighter and smaller. The above value is further 4 ≤ P Ｂ / P Ｍ We can set it to ≤ 10, and furthermore, 4.5 ≤ P Ｂ / P Ｍ We can set it to ≤9.8, and furthermore, 5.0 ≤ P Ｂ / P Ｍ We can set it to ≤9.6, and furthermore, 5.5 ≤ P Ｂ / P Ｍ It can be set to ≤ 9.4.

[0069] Furthermore, in the above puncture test, the amount of energy absorbed (Nmm) before the maximum impact force (N) is applied is E １The amount of energy absorbed (Nmm) from the time the maximum impact force (N) is applied until the fracture point is reached is defined as E. ２ And this energy amount E １ and the amount of energy E ２ The total absorbed energy (Nmm) is E Ｔ In that case, E Ｔ E for ２ Percentage (E ２ / E Ｔ ) can be 70% or more. That is, the amount of energy E absorbed from the time the maximum impact force (N) is applied until the point of fracture. ２ This means that the proportion of (Nmm) to the total absorbed energy is 70% or more (usually 90% or less). In other words, the amount of energy absorbed from the time a crack is formed due to the impact input until fracture occurs is 2.3 times or more the amount of energy absorbed until the crack is formed. Thus, this fiber-reinforced material and this structure can absorb a great deal of energy during crack propagation, and can exhibit excellent impact absorption before fracture. The above value further means 70 ≤ E ２ / E Ｔ (%) ≤ 90, and furthermore, 70.5 ≤ E ２ / E Ｔ (%) ≤ 88. In particular, in this fiber-reinforced material and this structure, under test conditions of striker speed of 4 m / s (i.e., high-speed impact input), furthermore, 72 ≤ E ２ / E Ｔ (%) can be set to ≤ 87, and furthermore, 74 ≤ E ２ / E Ｔ (%) ≤ 86, and furthermore, 76 ≤ E ２ / E Ｔ (%) can be set to ≤ 85.

[0070] Furthermore, the puncture test described above conforms to JIS K7211-2. In this test, the test specimen (fiber-reinforced material 10) is prepared as a fiber aggregate 15 with a basis weight of 200 g / m². ２ Using a carbon fiber woven fabric, the matrix material 12 has a basis weight of 600 g / m ２A fiber-reinforced material 10 (thickness in the range of 0.5 to 0.8 mm) obtained using the thermoplastic resin composition is used. Furthermore, in the puncture test apparatus, the above test specimen is fixed horizontally to a predetermined chuck, and the test is performed by launching a striker (load capacity 20 kN) that is a round bar shape with a diameter of 1 / 2 inch (12.7 mm) and a hemispherical tip from vertically above at a striker speed of 1 m / s to 4 m / s. By recording the impact force (N) and the resulting displacement (mm) during this test, the above parameters can be calculated (for more details, follow the test conditions of the examples described later).

[0071] [2] Structure The structure (50) of the present invention consists of the fiber-reinforced material (10) of the present invention described above. That is, the structure 50 can be said to be an attachment of the fiber-reinforced material 10. More specifically, examples include a structure 50 in which a predetermined shape (including a flat plate shape) is given to the fiber-reinforced material 10, and a structure 50 in which the unnecessary parts around the fiber-reinforced material 10 are cut off.

[0072] The shape, size, and thickness of this structure 50 are not particularly limited, nor are its uses particularly limited. This structure can be used, for example, as exterior material, interior material, structural material (body shell, vehicle body, aircraft fuselage), and shock absorber for automobiles, railway vehicles, ships, and airplanes. Among these, automotive products include automotive exterior material, automotive interior material, automotive structural material, automotive shock absorber, and engine compartment components. Specifically, these include bumpers, spoilers, cowlings, front grilles, garnishes, bonnets, trunk lids, cowl louvers, fender panels, rocker moldings, door panels, roof panels, instrument panels, center clusters, door trims, quarter trims, roof linings, pillar garnishes, deck trims, tonneau boards, package trays, dashboards, console boxes, kicking plates, switch bases, seat backboards, seat frames, armrests, sun visors, intake manifolds, engine head covers, engine undercovers, oil filter housings, housings for in-vehicle electronic components (ECUs, TV monitors, etc.), air filter boxes, energy absorbers such as lash boxes, and body shell components such as front end modules.

[0073] Furthermore, examples include interior, exterior, and structural materials for buildings and furniture. Specifically, it can be used for door coverings, door structural materials, coverings and structural materials for various furniture (desks, chairs, shelves, chests of drawers, etc.), as well as for unit bathrooms and septic tanks. It can also be used for packaging, containers (trays, etc.), protective components, and partition components. In addition, it can be used for molded bodies such as casings and structures for home appliances (flat-screen TVs, refrigerators, washing machines, vacuum cleaners, mobile phones, portable game consoles, laptop computers, etc.).

[0074] Furthermore, if the fibers 15 are short fibers, the short fibers can be incorporated into the matrix material as described above to form pellets. In this case, the method of manufacturing the fiber-reinforced material is not limited; for example, the thermoplastic resin composition that will become the matrix material 12 and the fibers 15 can be mixed and then formed into pellets to obtain the above-mentioned pellets. Alternatively, the fibers 15 may be incorporated during the preparation of the thermoplastic resin composition. For example, the above-mentioned pellets can be obtained by melt-kneading a polyolefin resin containing the fibers 15 with a melt-kneaded mixture of a polyamide resin and a modified elastomer, and then forming the resulting composition into pellets.

[0075] [3] Method for Manufacturing Fiber-Reinforced Materials and Structures The method for manufacturing fiber-reinforced materials and structures is not limited, but they can be manufactured by the following methods (1) to (7). (1) The fiber-reinforced materials and structures can be manufactured by molding a thermoplastic resin composition containing fibers (short fibers). That is, for example, the fiber-reinforced materials and structures can be manufactured by molding pellets (injection molding pellets) in which the aforementioned short fibers are contained in a matrix material. Known methods can be used for molding in this case. For example, injection molding, extrusion molding, blow molding, and molding methods combining these can be used.

[0076] (2) The fiber-reinforced material and the structure can be manufactured by laminating a fiber aggregate (for example, in the form of a film, sheet, mat, or plate) and a film made of a thermoplastic resin composition (which may be in the form of a sheet), heating and compressing the laminated layers to impregnate the fiber aggregate with the softened or melted thermoplastic resin composition, and then cooling (or air cooling) to solidify the thermoplastic resin composition. In the above lamination, one layer of fiber aggregate and one layer of thermoplastic resin composition film may be laminated, or one layer of fiber aggregate may be sandwiched between two layers of thermoplastic resin composition film and laminated. Furthermore, after obtaining a plate-shaped structure, it can be heated and reshaped to create a structure with a more complex shape.

[0077] (3) The fiber-reinforced material and the structure can be manufactured by sprinkling a powder made of a thermoplastic resin composition onto one side (usually the top) of a fiber aggregate (for example, a film, sheet, mat, or plate) and then heating and compressing it to soften or melt the thermoplastic resin composition within the fiber aggregate, and then cooling (or air cooling) to solidify the thermoplastic resin composition within the fiber aggregate. The powder can be vibrated to make it easier to disperse within the fiber aggregate. In this case as well, after obtaining a plate-shaped structure, it can be heated and reshaped to create a structure with a more complex shape.

[0078] (4) The fiber-reinforced material and the structure can be manufactured by mixing constituent fibers that form a fiber aggregate with thermoplastic resin composition fibers obtained by processing a thermoplastic resin composition into fibers, forming them into a mat (for example, by depositing them using an air array or the like), then heating and compressing to soften or melt only the thermoplastic resin composition fibers, and then cooling (or air cooling) to solidify the thermoplastic resin composition. In this case as well, after obtaining a plate-like structure, it is also possible to heat and reshape it to create a structure with a more complex shape.

[0079] (5) The fiber-reinforced material and the structure can be manufactured by dispersing constituent fibers that form a fiber aggregate and thermoplastic resin composition fibers obtained by processing a thermoplastic resin composition into fibers in a liquid, forming the constituent fibers and thermoplastic resin composition fibers in the dispersion into a mat shape by a papermaking method, then heating and compressing to soften or melt only the thermoplastic resin composition fibers, and then cooling (or air cooling) to solidify the thermoplastic resin composition.

[0080] (6) The fiber-reinforced material and the structure can be manufactured by forming a desired fiber aggregate using core-sheath fibers (i.e., the core material is the constituent fiber and the sheath material is the thermoplastic resin composition) in which the surface of the constituent fibers that will form the fiber aggregate is coated with a thermoplastic resin composition, then heating and compressing to soften or melt only the sheath material (thermoplastic resin composition), and then cooling (or air cooling) to solidify the thermoplastic resin composition. The fiber aggregate that can be formed using core-sheath fibers can be woven fabrics, knitted fabrics, nonwoven fabrics, etc., obtained by weaving, knitting, or nonwoven fabrication (for example, by depositing them in a mat shape using an air ray, etc.). In this case as well, after obtaining a plate-like structure, it is possible to heat and reshape it to create a structure with a more complex shape.

[0081] (7) The fiber-reinforced material and the structure can be manufactured by spraying a liquid thermoplastic resin composition onto a fiber aggregate (for example, a fiber aggregate in which fibers (long fibers) are aligned in one direction, or a fiber aggregate as a woven fabric), and then laminating the fiber aggregates coated with the liquid resin composition, or by molding them while laminating (Tape Laying System).

[0082] Furthermore, the thermoplastic resin used in the present invention may be prepared in any way, but it can be obtained by melt-kneading a molten mixture of a polyamide resin and a modified elastomer, and a polyolefin resin. That is, it is preferable to pre-melt-knead the polyamide resin and the modified elastomer separately from the polyolefin resin to obtain a molten mixture, and then melt-knead this molten mixture with the polyolefin resin to obtain a thermoplastic resin composition. It is thought that by forming a molten mixture of polyamide resin and modified elastomer in this way, the reactive groups of the modified elastomer are added to the surface of the polyamide resin, and polyamide resin particles to which the modified elastomer reactants are bound are formed. Further kneading then shears the polyamide resin particles to which the modified elastomer reactants are bound, and the surface of the unreacted polyamide resin is exposed. It is then thought that the unreacted modified elastomer reacts further with this unreacted surface. In this way, polyamide resin particles to which modified elastomer reactants are bound are sheared, exposing the surface of the unreacted polyamide resin. By repeatedly reacting the unreacted modified elastomer with this unreacted surface, it is thought that smaller polyamide resin particles to which modified elastomer reactants are bound can be stably formed without relying on high shear. The above-mentioned molten mixture may be a composition in a molten state, a composition in a softened state, or a solidified product obtained by pelletizing or the like.

[0083] Any type of melting and kneading apparatus can be used for the preparation of the above-mentioned molten mixture and for the melting and kneading of this molten mixture with the polyolefin resin. For example, an extruder (single-screw extruder, twin-screw compounding extruder, etc.), a kneader, a mixer (high-speed fluid mixer, paddle mixer, ribbon mixer, etc.) can be used. One type of apparatus may be used, or two or more types may be used in combination. When two or more types are used, they may be operated continuously or in batches. Furthermore, each raw material may be mixed all at once, or added in multiple stages (multi-stage compounding) and mixed. In addition, the melting and kneading temperature of the polyamide resin and the modified elastomer is not limited, but for example, 190°C to 350°C is preferred, 200°C to 330°C is more preferred, and 205°C to 310°C is even more preferred. On the other hand, the melt-mixing temperature of the polyamide resin and modified elastomer mixture with the polyolefin resin is not limited, but for example, 190°C to 350°C is preferred, 200°C to 300°C is more preferred, and 205°C to 260°C is even more preferred.

[0084] The present invention will be specifically described below with reference to examples. [1] Preparation of fiber-reinforced material <1> Fiber-reinforced material of Example 1 (1) Preparation of film made of thermoplastic resin composition After dry blending the following polyamide resin pellets and the following modified elastomer pellets, the mixture was put into a twin-screw molten compounding extruder and melt-kneaded at a mixing temperature of 210°C, and pellets consisting of a molten compound of polyamide resin and modified elastomer were obtained via a pelletizer. Furthermore, the above pellets (pellets consisting of a molten compound of polyamide resin and modified elastomer) and the following polyolefin resin pellets were dry blended, put into a twin-screw molten compounding extruder and melt-kneaded at a mixing temperature of 210°C, and pellets consisting of a basis weight of 300 g / m² were obtained via a T-die extruder. ２A film made from the following thermoplastic resin composition was obtained. The mixing ratio of polyolefin resin, polyamide resin, and modified elastomer was 55:25:20 by mass. • Polyolefin resin: Polypropylene resin, homopolymer, manufactured by Nippon Polypropylene Co., Ltd., product name "Novatec MA1B", weight-average molecular weight 312,000, melting point 165°C) • Polyamide resin: Nylon 11 resin, manufactured by Arkema K.K., product name "Rilsan BMN O", weight-average molecular weight 18,000, melting point 190°C • Modified elastomer: Maleic anhydride-modified ethylene-butene copolymer (modified EBR), manufactured by Mitsui Chemicals, Inc., product name "Tafmer MH7020"

[0085] (2) Preparation of fiber-reinforced material Carbon fibers (3K: multifilament containing 3000 single fibers) are woven in a plain weave with a basis weight of 200 g / m ２ A carbon fiber fabric was prepared as a fiber aggregate (15). One sheet of the fiber aggregate was placed in the center, and one thermoplastic resin composition film obtained in (1) was placed above and below it, and the temperature was set to 240°C and the pressure was set to 1 × 10 ７ N / m ２ After heating and compressing for 120 seconds under these conditions, further pressurization was performed at room temperature (approximately 25°C) and a pressure of 5 × 10⁻¹⁰. ６ N / m ２ Cooling and compression were performed for 120 seconds under these conditions to obtain the fiber-reinforced material of Example 1 (i.e., a plate-shaped structure) (thickness 0.6 mm).

[0086] <2> Fiber-reinforced material of Comparative Example 1 (1) Preparation of polyolefin resin film Using a T-die extruder, the following polyolefin resin was extruded to a basis weight of 300 g / m ２ It was formed into a film. • Polyolefin resin: Polypropylene resin, block polymer, manufactured by Prime Polymer Co., Ltd., product name "J-452HP", melting point 165℃ (2) Preparation of fiber-reinforced material Same as in (1) (2) above, basis weight 200 g / m ２ A carbon fiber fabric (3K multifilament, plain weave) was prepared as a fiber aggregate (15). One sheet of this fiber aggregate was placed in the center, and one sheet each of the polyolefin resin film obtained in (1) above was placed above and below it, and the temperature was set to 240°C and the pressure was set to 1 × 10⁻⁶.７ N / m ２ After heating and compressing for 120 seconds under these conditions, further pressurization was performed at room temperature (approximately 25°C) and a pressure of 5 × 10⁻¹⁰. ６ N / m ２ Cooling and compression were performed for 120 seconds under these conditions to obtain the fiber-reinforced material (thickness 0.6 mm) of Comparative Example 1.

[0087] <3> Fiber-reinforced material of Comparative Example 2 (1) Preparation of polyamide resin film Using a T-die extruder, the following polyamide resin was extruded to a basis weight of 300 g / m ２ It was formed into a film. Polyamide resin: Nylon 6 resin, manufactured by Toray Industries, Inc., product name "Amiran CM1021FS", melting point 225℃ (2) Preparation of fiber-reinforced material Same as in (1) (2) above, basis weight 200 g / m ２ A carbon fiber fabric (3K multifilament, plain weave) was prepared as a fiber aggregate (15). One sheet of this fiber aggregate was placed in the center, and one polyamide resin film obtained in (1) above was placed above and below it, and the temperature was set to 260°C and the pressure was set to 1 × 10⁻⁶. ７ N / m ２ After heating and compressing for 120 seconds under these conditions, further pressurization was performed at room temperature (approximately 25°C) and a pressure of 5 × 10⁻¹⁰. ６ N / m ２ Cooling and compression were performed for 120 seconds under these conditions to obtain the fiber-reinforced material (thickness 0.6 mm) of Comparative Example 2.

[0088] [2] Evaluation of fiber-reinforced materials (1) Puncture test (strike speed 1 m / sec) A puncture test was performed in accordance with JIS K7211-2. Test specimens (fiber-reinforced materials) were made from test pieces (120 mm x 150 mm) cut from each of the fiber-reinforced materials of "Example 1", "Comparative Example 1", and "Comparative Example 2" obtained in [1] above. Specifically, the above-mentioned test specimens were horizontally fixed to the chuck of a puncture test apparatus (Shimadzu Corporation, high-speed impact tester, model "EHF-22H-20L"), and a striker (load capacity 20kN) with a diameter of 1 / 2 inch (12.7 mm) and a hemispherical tip was launched vertically from above at a striker speed of 1 m / s. The impact force (N) and the resulting displacement (mm) were recorded. These results are shown as charts in Figure 5. (2) Puncture test (striker speed 4 m / s) The impact force (N) and the resulting displacement (mm) were recorded in the same manner as in (1) above, except that the striker speed was set to 4 m / s. These results are shown as charts in Figure 6.

[0089] (3) Evaluation method The chart obtained from the puncture test in (1) and (2) above is evaluated as follows P Ｍ , P Ｂ , E １ , E ２ , E Ｔ Set it. "P Ｍ (mm): P is the displacement (mm) at which the maximum impact force (N) in each test was obtained from the chart obtained in (1) above. Ｍ This is shown in Figures 5 and 6. It is thought that cracks are generated when this maximum impact force (N) is achieved. Ｂ (mm): Among the chart obtained in (1) above, the displacement (mm) immediately before the impact force (N) becomes 0 N or less over the range of displacement of 2 mm or more is the fracture point P Ｂ This is shown in Figures 5 and 6. This P Ｍ From P Ｂ It is believed that crack propagation occurs when reaching this point.

[0090] "E １ (Nmm)": In the chart obtained in (1) above, PＭ A line segment L parallel to the Y-axis passing through [the specified point]. Ｅ (The dotted line L on the left side in Figures 5 and 6) Ｅ When this line segment L is drawn (see reference), Ｅ The region located to the left (the region with less displacement) is E １ This is shown in Figures 5 and 6. Furthermore, region E １ The area was calculated and is shown in Figures 5 and 6. ２ (Nmm)": In the chart obtained in (1) above, P Ｍ A line segment L parallel to the Y-axis passing through [the specified point]. Ｅ (The dotted line L on the left side in Figures 5 and 6) Ｅ When this line segment L is drawn (see reference), Ｅ The region located to the right (the region with greater displacement) is E ２ This is shown in Figures 5 and 6. Furthermore, region E ２ The area was calculated and is shown in Figures 5 and 6. Ｔ (Nmm)”: Area E １ The area and region E ２ The area of ​​and the total area of ​​are E Ｔ This is shown in Figures 5 and 6. Note that in Figures 5 and 6, line segment L Ｂ (The dotted line L on the right in Figures 5 and 6) Ｂ (See P) Ｂ This is a line segment parallel to the Y-axis that passes through [the specified point].

[0091] [3] Effects of the Examples From Figures 5 and 6, in Comparative Example 1 in which polyolefin resin was used as the matrix material 12, P Ｂ / P Ｍ = 2.94, and in Comparative Example 1-2 (strike speed 4 m / sec), P Ｂ / P Ｍ = 2.56. In other words, it can be seen that the amount of displacement required for crack propagation is small compared to the amount of displacement until crack initiation. Furthermore, in Comparative Example 2, in which polyamide resin was used as the matrix material 12, P was observed in Comparative Example 2-1 (strike speed 1 m / sec). Ｂ / P Ｍ = 8.75, and in Comparative Example 2-2 (strike speed 4 m / sec), P Ｂ / PＭ = 5.31. In other words, it can be seen that the amount of displacement required for crack propagation is large compared to the amount of displacement until crack initiation. However, at a striker speed of 1 m / s, P Ｂ / P Ｍ It is large, but at a striker speed of 4 m / s, P Ｂ / P Ｍ It can be seen that it is shrinking. Also, at a striker speed of 4 m / s, P Ｍ The value is 2.81, indicating that the amount of displacement required to cause cracks is small. In other words, polyamide resin can exhibit high shock absorption capacity against impacts applied at low speeds, but the shock absorption capacity tends to decrease as the impact is applied at higher speeds.

[0092] In contrast, in Example 1, where a predetermined thermoplastic resin composition was used as the matrix material 12, P was observed in Example 1-1 (strike speed 1 m / sec). Ｂ / P Ｍ = 5.96, and in Example 1-2 (strike speed 4 m / sec), P Ｂ / P Ｍ = 7.17. Furthermore, in Example 1-1, P Ｍ = 4.56, in Example 1-2 P Ｍ The value is 3.83, indicating that the amount of displacement required to initiate a crack is large, regardless of the striker speed. In other words, by using a predetermined thermoplastic resin composition, it is possible to achieve high shock absorption capacity regardless of the speed of the impact applied, from low to high speeds. This result suggests that the fracture in Examples 1-1 and 1-2 was ductile fracture.

[0093] Furthermore, as can be seen from Figures 5 and 6, in Comparative Example 1, where polyolefin resin was used as the matrix material 12, E was observed in Comparative Example 1-1 (strike speed 1 m / sec). ２ / E Ｔ ×100 = 57.8%, and in Comparative Example 1-2 (strike speed 4 m / sec), E ２ / E Ｔ×100 = 77.6%. In other words, it can be seen that the amount of energy that can be absorbed during crack propagation is small compared to the amount of displacement until crack initiation. In Comparative Example 2, in which polyamide resin was used as the matrix material 12, E was obtained in Comparative Example 2-1 (strike speed 1 m / sec). ２ / E Ｔ ×100 = 71.7%, and in Comparative Example 2-2 (strike speed 4 m / sec), E ２ / E Ｔ × 100 = 68.5%. This means that the amount of energy that can be absorbed during crack propagation is large compared to the amount of displacement until crack initiation. However, at a striker speed of 1 m / s, E ２ / E Ｔ The proportion is large, but at a striker speed of 4 m / s, E ２ / E Ｔ It can be seen that the proportion is decreasing.

[0094] In contrast, in Example 1, where a predetermined thermoplastic resin composition was used as the matrix material 12, E was observed in Example 1-1 (strike speed 1 m / sec). ２ / E Ｔ ×100 = 71.3%, and in Example 1-2 (strike speed 4 m / sec), E ２ / E Ｔ × 100 = 82.0%, indicating that a large amount of energy can be absorbed before crack formation, regardless of the striker speed. In other words, by using a specific thermoplastic resin composition, high shock absorption capacity can be achieved regardless of the speed of the impact applied, from low to high speeds.

[0095] The examples described herein are for illustrative purposes only and should not be construed as limiting the invention. Although the invention has been described with examples of typical embodiments, the language used in the description and illustrations of the invention should be understood as descriptive and illustrative, not limiting. As detailed herein, modifications are possible within the scope or spirit of the invention without departing in any way. While specific structures, materials, and examples have been referenced in this detailed description of the invention, the invention is not intended to be limited to the disclosures herein, but rather to encompass all functionally equivalent structures, methods, and uses within the scope of the claims.

[0096] 10; Fiber-reinforced material, 12; Matrix material, 15; Fiber, fiber aggregate, 50; Structure, A; Continuous phase, B; Dispersed phase, B １ ; Continuous phase (continuous phase within dispersed phase B), B ２ ; Microdispersed phase (dispersed phase within dispersed phase B), A １ A ２ ; Continuous phase, B Ａ１ , B Ａ２ ; dispersed phase, B Ａ１１ ; Continuous phase (dispersed phase B) Ａ１ (Continuous phase within) B Ａ１２ ; Finely dispersed phase (dispersed phase B Ａ１ (The dispersed phase within).

Claims

DEPCT631. Fiber-reinforced material consisting of: fibers, and a matrix material used to coat the fibers, where the matrix material is a thermoplastic resin composition obtained by mixing polyolefin resin, polyamide resin, and a modified elastomer with reactive groups that react with the polyamide resin.

2. Fiber-reinforced material under Reputation 1 where the fibers are a fiber assembly.

3. Fiber-reinforced material under Reputation 1 or 2 where, when the puncture test is performed at an impact velocity of 1 m / s or more but 4 m / s or less, and when the deflection (mm) at maximum impact (N) is defined as PM, and the maximum deflection at break (mm) is defined as PB, then the PB / PM ratio is greater than or equal to 4. 4.Fiber-reinforced material under Reputation 3 where the amount of energy (N / mm²) absorbed before the maximum impact force (N) is defined as E1, the amount of energy (N / mm²) absorbed after the maximum impact force (N) and before fracture is defined as E2, and the total amount of energy absorbed (N / mm²), which is the sum of the energy amounts E1 and E2, is defined as ET, and the ratio of E2 to ET (E2 / ET) is 70 percent or more.

5. Fiber-reinforced material under any one of Reputations 1 through 4 where the fiber bundle is a woven / knit fabric.

6. Fiber-reinforced material under any one of Reputations 1 through 4 where the fiber bundle is a non-woven fabric.

7. Fiber-reinforced materials under any of the claims 1 through 6 where the thermoplastic resin composition has a continuous phase (A) containing the polyolefin resin, and a dispersed phase (B) dispersed in the continuous phase (A) and containing the polyamide resin.8.Fiber-reinforced material under claim 7 in which the dispersed phase (B) contains additional modified elastic material, and the dispersed phase (B) contains a continuation phase (B1) containing polyamide resin and a fine dispersed phase (B2) dispersed in the continuation phase (B1) and containing modified elastic material.

9. Product (article) which is composed of fiber-reinforced material under any one of claims 1 through 8.