Fiber-reinforced resin molding materials and molded articles

Abstract

A fiber-reinforced resin molding material comprises reinforcing fibers (A) and thermoplastic resin (B). Relative to a total of 100 parts by weight of (A) and (B), the fiber-reinforced resin molding material comprises 1 to 30 parts by weight of reinforcing fibers (A) and 70 to 99 parts by weight of thermoplastic resin (B). The reinforcing fibers (A) comprise reinforcing fibers (A-1) and bundled reinforcing fibers (A-2). The reinforcing fibers (A-1) have a length of 3 to 15 mm and are aligned with the longitudinal direction of the molding material. The bundled reinforcing fibers (A-2) are composed of 10 or more single yarns with a length of 0.5 to 2.9 mm. This provides fiber-reinforced resin molding materials and fiber-reinforced resin molded articles that achieve excellent flowability, mechanical properties, and dimensional accuracy.

Description

Technical Field

[0001] This invention relates to a molding material comprising reinforcing fibers and thermoplastic resin, and a molded article comprising reinforcing fibers and thermoplastic resin. Prior Technology

[0002] Molding materials using continuous reinforcing fibers and thermoplastic resins as a matrix are known to exist in various forms, including thermoplastic prepregs, yarns, and glass mats (GMT). These molding materials, by utilizing the properties of thermoplastic resins, are easy to mold, do not require the storage load of thermosetting resins, and produce molded articles with high toughness. In particular, molding materials processed into granules are suitable for economical and productive molding methods such as injection molding or stamping, making them useful as industrial materials.

[0003] Patent Document 1 discloses pulverizing a molding material composed of reinforcing fibers and thermoplastic resin, and then injecting the resulting molding material containing fiber-reinforced thermoplastic resin molding material into a molded article to obtain a molded article with excellent mechanical properties and flowability. Furthermore, Patent Documents 2 and 3 disclose obtaining molded articles with excellent mechanical properties and appearance quality by combining two types of reinforcing fibers—one with long fiber length and the other with short fiber length—with thermoplastic resin and then injecting them into the mold. [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2006-181776 [Patent Document 2] Japanese Patent Application Publication No. 2012-116917 [Patent Document 3] Japanese Patent Application Publication No. 4-175108 Summary of the Invention

[0005] [The problem the invention aims to solve] However, in recent years, with the miniaturization, thinning, and increasing complexity of molded products, higher precision formability is required for molding materials. A high degree of balance is needed to achieve excellent flowability and mechanical properties, as well as dimensional accuracy, for small, thin-walled, and complex molded products. Previously, thermoplastic resin molding materials containing reinforcing fibers suffered from poor flowability due to the increased length of the reinforcing fibers. On the other hand, while short reinforcing fibers offer excellent flowability, they are prone to breakage during injection molding, resulting in reduced mechanical properties and dimensional accuracy of the molded products. These factors are difficult to balance. Therefore, applications requiring small, thin-walled, and complex molded products must incorporate long reinforcing fibers with excellent mechanical properties and superior flowability.

[0006] Therefore, the objective of this invention is to provide a fiber-reinforced resin molding material and fiber-reinforced resin molded article that can achieve both excellent flowability, mechanical properties and dimensional accuracy, in view of the above problems and necessities. [Methods used to solve problems]

[0007] To address the aforementioned issues, the present invention has the following configuration. (1) A fiber-reinforced resin molding material, comprising reinforcing fibers (A) and thermoplastic resin (B), wherein... Relative to a total of 100 parts by weight of (A) and (B), the fiber-reinforced resin molding material comprises 1 to 30 parts by weight of reinforcing fiber (A) and 70 to 99 parts by weight of thermoplastic resin (B). The aforementioned reinforcing fiber (A) comprises reinforcing fiber (A-1) and bundled reinforcing fiber (A-2). The aforementioned reinforcing fiber (A-1) has a length of 3-15 mm and is aligned with the longitudinal direction of the molding material. The length of the reinforcing fiber (A-1) is the same as the length of the molding material along its longitudinal direction. The aforementioned bundled reinforcing fiber (A-2) is composed of more than 10 single yarns with a length of 0.5 to 2.9 mm. (2) The fiber-reinforced resin molding material as described in (1), wherein The aforementioned fiber-reinforced resin molding materials include fiber-reinforced resin molding material (X) and fiber-reinforced resin molding material (Y). Fiber-reinforced resin molding material (X) comprises reinforcing fibers (A-1) and thermoplastic resin (B-1). The reinforcing fiber (A-1) and the fiber-reinforced resin molding material (X) are aligned in the same longitudinal direction. The fiber-reinforced resin molding material (Y) comprises bundled reinforcing fibers (A-2) and thermoplastic resin (B-2). (3) The fiber-reinforced resin molding material as described in (1) or (2), wherein The aforementioned fiber-reinforced resin molding material has a core-sheath structure. The core structure of the aforementioned core-sheath structure includes reinforcing fibers (A-1), and the reinforcing fibers (A-1) are aligned with the longitudinal direction of the forming material. The sheath structure of the aforementioned core-sheath structure is a fiber-reinforced resin composition (C) comprising bundled reinforcing fibers (A-2) and thermoplastic resin (B). The aforementioned sheath structure covers the aforementioned core structure. (4) The fiber-reinforced resin molding material described in any of (1) to (3), wherein the aforementioned reinforcing fiber (A-1) and bundled reinforcing fiber (A-2) are both carbon fibers. (5) The fiber-reinforced resin molding material described in any of (1) to (4) wherein, relative to 100 parts by weight of the reinforcing fiber (A), the content of the aforementioned reinforcing fiber (A-1) and bundled reinforcing fiber (A-2) is 50 to 99 parts by weight of the reinforcing fiber (A-1) and 1 to 50 parts by weight of the bundled reinforcing fiber (A-2). (6) The fiber-reinforced resin molding material described in any of (1) to (5), wherein the resin component (D) is attached to the surface of the fiber bundle of the aforementioned bundle-shaped reinforcing fiber (A-2). (7) The fiber-reinforced resin molding material as described in (6), wherein the aforementioned resin component (D) is a thermosetting resin, and is contained in 7 or more parts by weight relative to 100 parts by weight of bundled reinforcing fibers (A-2). (8) The fiber-reinforced resin molding material described in any one of (1) to (7), wherein the aforementioned thermoplastic resin (B) includes at least one selected from polyamide resin, polycarbonate resin, polyphenylene sulfide resin and polypropylene resin. (9) A fiber-reinforced resin molded article, comprising reinforcing fibers (A') and thermoplastic resin (B), wherein... Relative to a total of 100 parts by weight of (A') and (B), the fiber-reinforced resin molded article comprises 1 to 30 parts by weight of reinforcing fiber (A') and 70 to 99 parts by weight of thermoplastic resin (B). The weight-average fiber length Lw(A') of the reinforcing fiber (A') is 0.1~2.9 mm. The reinforcing fiber (A') comprises a bundle of reinforcing fibers (A-2') consisting of 10 or more single yarns with a length of 0.5 to 2.9 mm. (10) The fiber-reinforced resin molded article as described in (9) wherein the proportion of the aforementioned reinforcing fibers (A') having a fiber length of 0.3 to 1.0 mm is 40% or more. (11) The fiber-reinforced resin molded article as described in (9) or (10), wherein the aforementioned bundled reinforcing fiber (A-2') is contained in 1 to 50 parts by weight relative to 100 parts by weight of reinforcing fiber (A'). (12) The fiber-reinforced resin molded article described in any of (9) to (11), wherein the aforementioned reinforcing fiber (A') is carbon fiber. (13) A fiber-reinforced resin molded article as described in any of (9) to (12), wherein the resin component (D) is attached to the surface of the fiber bundle of the aforementioned bundle-shaped reinforcing fiber (A-2'). (14) The fiber-reinforced resin molded article as described in (13), wherein the aforementioned resin component (D) is a thermosetting resin, and is contained in 7 or more parts by weight relative to 100 parts by weight of bundled reinforcing fibers (A-2'). (15) A fiber-reinforced resin molded article as described in any of (9) to (14), wherein the aforementioned thermoplastic resin (B) includes at least one selected from polyamide resin, polycarbonate resin, polyphenylene sulfide resin and polypropylene resin. [Effects of the Invention]

[0008] According to the present invention, a molding material that can achieve both excellent flowability and mechanical properties as well as dimensional accuracy can be obtained. The molding material of the present invention has excellent flowability during molding and can easily manufacture molded articles with excellent mechanical properties and dimensional accuracy. Therefore, it is not limited to molding methods such as injection molding, transfer molding, blow molding, and insert molding, but can also be applied to a wide range of molding methods such as plunger molding, press molding, and stamping.

[0009] Examples of molded articles obtained by molding the molding material of the present invention include: automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder heads, bearing retainers, intake manifolds, and pedals; semiconductor and liquid crystal manufacturing equipment parts such as silicon wafer carriers, IC chip trays, electrolytic capacitor trays, and insulating films; industrial machinery parts such as compressor parts such as pumps, valves, and seals, and aircraft cabin interior parts; medical device parts such as sterilization equipment, tubing, and piping, and food and beverage manufacturing equipment parts. Furthermore, by using the molding material of the present invention, molded articles with thin walls of 0.5 to 2 mm can be obtained relatively easily. Examples of applications requiring such thin-walled molding include: keyboard supports and other components for electrical and electronic instruments, such as those used inside personal computers to support the keyboard. Such electrical and electronic instrument components are more suitable when using conductive carbon fibers in the reinforcing fibers, which impart electromagnetic wave shielding properties. Simple Explanation of the Diagram

[0010] Figure 1 is a schematic diagram showing an example of the shape of a cross-section of the molding material in the axial direction according to one embodiment of the present invention. Figure 2 is a schematic diagram showing an example of the shape of a cross-section of a molding material in the axial direction according to another embodiment of the present invention. Figure 3 is a schematic diagram showing an example of the shape of a molding material in a cross-section orthogonal to the axis in another embodiment of the present invention. Figure 4 is a schematic diagram showing an example of the shape of a molding material in a cross-section orthogonal to the axis in another embodiment of the present invention. Figure 5 is a schematic diagram showing an example of the shape of a molding material in a cross-section orthogonal to the axis in another embodiment of the present invention. Figure 6 is a schematic perspective view showing an example of the shape of a molding material in another embodiment of the present invention. Figure 7 is a schematic perspective view showing an example of the shape of a molding material in another embodiment of the present invention. Figure 8 is a schematic perspective view showing an example of the shape of a molding material in another embodiment of the present invention. Implementation

[0011] [The form in which the invention is carried out] The present invention, together with its embodiments, will now be described in detail.

[0012] <Forming Materials> The molding material of this invention comprises reinforcing fibers (A) and thermoplastic resin (B). By including reinforcing fibers (A), the long fiber length of the reinforcing fibers can be maintained, thus exhibiting excellent mechanical properties.

[0013] [Reinforced Fiber (A)] Explain the reinforcing fiber (A) in this invention. There are no particular limitations on the type of reinforcing fiber (A) used in this invention. For example, carbon fiber, glass fiber, aromatic polyamide fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, natural fiber, mineral fiber, etc., can be used, and one or more of these can be used together. From the viewpoint of obtaining lightweight molded articles with high strength and high modulus of elasticity, PAN (polyacrylonitrile) based, pitch-based, and filament-based carbon fibers are preferred. In particular, from the viewpoint of high strength, reinforcing fibers with a tensile strength of 4000 MPa or higher are preferred, and more preferably 5000 MPa or higher. From the viewpoint of high modulus of elasticity, reinforcing fibers with a tensile modulus of elasticity of 200 GPa or higher are preferred, and more preferably 400 GPa or higher. In particular, reinforcing fibers with an elastic modulus of 400 GPa or higher, which are more difficult to maintain in terms of fiber length, are preferred because they better demonstrate the effects of the molding material of this invention described later.

[0014] Furthermore, from the viewpoint of improving the economy of the resulting molded article, glass fiber is more suitable, especially considering the balance between mechanical properties and economy; a combination of carbon fiber and glass fiber is preferable. Moreover, from the viewpoint of improving the impact absorption or shape retention of the resulting molded article, aromatic polyamide fiber is more suitable, especially considering the balance between mechanical properties and impact absorption; a combination of carbon fiber and aromatic polyamide fiber is preferable. Furthermore, from the viewpoint of improving the electrical conductivity of the resulting molded article, reinforcing fibers coated with metals such as nickel, copper, and ytterbium, as well as pitch-based carbon fibers, can also be used.

[0015] It is preferable that the bubbling agent is attached to the reinforcing fiber (A). This is because by attaching the bubbling agent to the reinforcing fiber (A), the processability of the reinforcing fiber during transfer and the processability during the manufacturing of molded materials can be improved. There is no particular limitation on the type of bubbling agent, but one or more bubbling agents such as epoxy resin, urethane resin, acrylic resin or various thermoplastic resins can be used together.

[0016] The amount of reinforcing fiber (A) relative to 100 parts by weight of molding material is preferably 1 to 30 parts by weight. More preferably, it is 2 to 25 parts by weight, and even more preferably, it is 5 to 20 parts by weight. When the amount of reinforcing fiber (A) is less than 1 part by weight, the mechanical properties and dimensional accuracy of the resulting molded article will be insufficient, and when it exceeds 30 parts by weight, the flowability will decrease.

[0017] The reinforcing fiber (A) of this invention comprises a reinforcing fiber (A-1) and a bundle of reinforcing fibers (A-2). The length of the reinforcing fiber (A-1) is preferably 3-15 mm, more preferably 5-10 mm. The reinforcing fiber (A-1) is preferably arranged with individual fibers in a unidirectional orientation. Examples of preferred configurations include unidirectional fiber bundles, bidirectional fiber bundles, and multidirectional fiber bundles, but from a productivity standpoint in manufacturing the molded material, unidirectional fiber bundles are preferred. From an economic perspective, a higher number of individual yarns in the reinforcing fiber (A) is more advantageous; when the molded material is formed, for example, into pellets, the number of individual fibers per pellet is preferably 10,000 or more. On the other hand, the more single yarns there are in the reinforcing fibers, the less favorable the impregnation of the matrix resin tends to be. Therefore, from the perspective of seeking both economy and impregnation, it is better to use more than 15,000 yarns and less than 100,000 yarns, and even better to use more than 20,000 yarns and less than 50,000 yarns.

[0018] Furthermore, the reinforcing fiber (A-1) is preferably such that, in the molding material, the reinforcing fiber (A-1) is aligned with the longitudinal direction of the molding material, and the length of the reinforcing fiber (A-1) is substantially the same as the length of the molding material. Here, "aligned with the longitudinal direction of the molding material" means that the axis of the long axis of the reinforcing fiber (A-1) and the axis of the long axis of the molding material point in the same direction, and the angular offset between the axes is preferably less than 20°, more preferably less than 10°, and even more preferably less than 5°. Also, "substantially the same length" means, for example, in a pellet-shaped molding material, that the reinforcing fiber (A-1) is not cut off along its length within the pellet, or that it substantially does not contain any reinforcing fiber (A-1) intentionally shorter than the total length of the pellet. Furthermore, the total length of the pellet is the length of the reinforcing fiber (A-1) in the alignment direction within the pellet. Since the reinforcing fiber (A-1) has substantially the same length as the molding material, the length of the reinforcing fiber in the molded article can be increased, resulting in excellent mechanical properties and dimensional accuracy.

[0019] The length of the bundled reinforcing fiber (A-2) is preferably 0.5~2.9 mm, more preferably 0.6~2.7 mm, and even more preferably 0.7~2.5 mm. When the length of the bundled reinforcing fiber (A-2) is less than 0.5 mm, it is unsuitable due to poor mechanical properties and dimensional accuracy of the molded product. On the other hand, when the length of the bundled reinforcing fiber (A-2) is longer than 2.9 mm, it is unsuitable due to poor flowability. Furthermore, the bundled reinforcing fiber (A-2) is composed of 10 or more reinforcing fiber yarns. The number of reinforcing fiber yarns constituting the bundled reinforcing fiber (A-2) is preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more. When the number of yarns in the bundled reinforcing fiber (A-2) is less than 10, fiber breakage will occur during injection molding, resulting in poor mechanical properties and dimensional accuracy of the molded product. There is no specific upper limit for the number of yarns per unit, but it is preferable to keep it below 100,000, and more preferably below 80,000. A yarn count exceeding 100,000 is not recommended due to the poor surface quality of the finished product.

[0020] The form of the bundled reinforcing fiber (A-2) used in melt mixing is not limited as long as it can be added to the melt mixing apparatus. Examples include pre-cut chopped strands, fragmented fibers, and continuous long fibers. From a production point of view, chopped strands are preferred. Chopped strands can be recycled by crushing the fiber-reinforced resin molded article and thermally decomposing the matrix resin. A well-known method can be used to obtain recycled chopped strands. For example, waste sheets that have been crushed and graded from the fiber-reinforced resin molded article are evenly spread on a metal tray, placed in an electric furnace, and heat-treated by introducing nitrogen gas into the furnace while maintaining the processing temperature at a specific temperature. Subsequently, similarly, heat-treated by introducing air into the furnace while maintaining the processing temperature at a specific temperature, can yield recycled chopped strands.

[0021] Furthermore, the optimal heat treatment temperature in the air environment during the heat treatment process is 300℃~700℃. If the heat treatment temperature in the air environment exceeds 700℃, the resin component (D) will completely disappear, leaving only reinforcing fibers. The bundled nature of the reinforcing fiber bundles (bundled reinforcing fibers (A-2)) will disappear, and they cannot remain as bundled reinforcing fibers. Therefore, fiber breakage increases, and mechanical properties or dimensional accuracy are poor, making this unsuitable. Conversely, if the heat treatment temperature is below 300℃, the resin component (D) will increase, leading to reduced toughness of the matrix resin and poor mechanical properties, making this also unsuitable.

[0022] Furthermore, it is preferable to perform the final heat treatment in an air environment. If the initial heat treatment is performed at 700°C for 2 hours in a nitrogen atmosphere, the resin component (D) will be 7 parts by weight or more. In an inert nitrogen atmosphere, even if heat treatment is performed for more than 2 hours, the resin component (D) will not change. By performing the final heat treatment in an active air environment, recycled short-cut strands with the desired resin component (D) can be obtained.

[0023] In this invention, a material that has been previously crushed into fiber-reinforced resin molded articles can be used. When crushing, considering subsequent processability, the maximum length of the crushed material is preferably reduced to less than 20 mm. As a crusher for such fiber-reinforced resin molded articles, a shear crusher, impact crusher, cutting crusher, or compression crusher can be used. Any crusher can be used, and combinations are also possible. Furthermore, as a classifier for the crushed products, a vibrating screen, rotary screen, or centrifugal screen can be used. It is preferable to use a crusher that is compatible with the crushing capacity of the crusher and the morphology of the crushed material.

[0024] The types of reinforcing fibers (A-1) and bundled reinforcing fibers (A-2) used in this invention are not particularly limited, and any filler material with a fibrous shape can be used. Specifically, examples include: glass fibers; PAN-based and pitch-based carbon fibers; metal fibers such as stainless steel fibers, aluminum fibers, and brass fibers; organic fibers such as aromatic polyamide fibers; fibrous and whisker-like fillers such as gypsum fibers, ceramic fibers, asbestos fibers, zirconium oxide fibers, alumina fibers, silicon dioxide fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, silicon nitride whiskers, wollastonite, and alumina silicates; and non-metallic fibers (glass fibers, aromatic polyamide fibers, polyester fibers, carbon fibers, etc.) coated with metals (nickel, copper, cobalt, silver, aluminum, iron, and their alloys). Among the aforementioned short fibrous fillers, PAN-based and pitch-based carbon fiber systems are preferred examples, with PAN-based carbon fibers being a particularly preferred example.

[0025] The preferred content of the reinforcing fiber (A-1) and the bundled reinforcing fiber (A-2) in this invention is: relative to 100 parts by weight of reinforcing fiber (A), it comprises 50 to 99 parts by weight of reinforcing fiber (A-1) and 1 to 50 parts by weight of bundled reinforcing fiber (A-2). If the content of the aforementioned reinforcing fiber (A-1) is less than 50 parts by weight, the mechanical properties and dimensional stability of the molded article are poor, and therefore it is undesirable. Furthermore, if the content of reinforcing fiber (A-1) exceeds 99 parts by weight, the flowability during injection molding is poor, and therefore it is undesirable. The content of reinforcing fiber (A-1) is more preferably 60 to 95 parts by weight, and even more preferably 70 to 90 parts by weight. If the content of the aforementioned bundled reinforcing fiber (A-2) is less than 1 part by weight, the mechanical properties and dimensional accuracy of the molded article are poor, and therefore it is undesirable. If the content of the aforementioned bundled reinforcing fiber (A-2) exceeds 50 parts by weight, the mechanical properties are poor, and therefore it is undesirable.

[0026] [Thermoplastic Resin (B)] The molding material of the present invention contains 70 to 99 parts by weight of thermoplastic resin (B) relative to a total of 100 parts by weight of reinforcing fiber (A) and thermoplastic resin (B).

[0027] In this invention, the thermoplastic resin (B) is preferably one with a molding temperature (melting temperature) of 200-450°C, and examples include: polyolefin resin, polystyrene resin, polyamide resin, halogenated vinyl resin, polyacetal resin, saturated polyester resin, polycarbonate resin, polyaryl ether resin, polyaryl ketone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyaryl ether ketone resin, polyether ether resin, polyphenylene sulfide ether resin, polyaryl ester resin, polyamide resin, etc., all of which are equivalent to electrical insulators. Two or more of these resins may also be used.

[0028] Among the aforementioned thermoplastic resins (B), polyolefin resins, polyamide resins, polycarbonate resins, and polyarylether resins that are lightweight and have an excellent balance of mechanical properties and formability are preferred.

[0029] The term "polyolefin resin" as used here includes both unmodified and modified resins. For example, unmodified polypropylene resin specifically refers to a homopolymer of propylene or a copolymer of propylene with at least one α-olefin, conjugated diene, or non-conjugated diene. Examples of α-olefins include: ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, and other α-olefins with 2 to 12 carbon atoms excluding propylene. Examples of conjugated and non-conjugated dienes include: butadiene, ethylbenzene, dicyclopentadiene, and 1,5-hexadiene. Two or more of these may also be used. Examples of suitable structural components for unmodified polypropylene resin include homopolymers of propylene, random or block copolymers of propylene with the aforementioned other monomers, and random or block copolymers of propylene with other thermoplastic monomers. Suitable examples include polypropylene, ethylene-propylene copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers. From the viewpoint of further improving the rigidity of the molded article, homopolymers of propylene are preferred; from the viewpoint of further improving the impact strength of the molded article, random or block copolymers of propylene with the aforementioned other monomers are preferred.

[0030] Furthermore, as a modified polypropylene resin, an acid-modified polypropylene resin is preferred, and more preferably a polypropylene resin having carboxylic acid groups and / or their salts bonded to the polymer chain. The aforementioned acid-modified polypropylene resin can be obtained by various methods. For example, it can be obtained by graft polymerization of monomers having neutralized or unneutralized carboxylic acid groups and / or monomers having saponified or unsaponified carboxylic acid esters onto a polypropylene resin.

[0031] Here, examples of monomers having neutralized or unneutralized carboxylic acid groups or having saponified or unsaponified carboxylic acid ester groups include: vinyl unsaturated carboxylic acids, their anhydrides, and esters thereof. Furthermore, examples of compounds having unsaturated vinyl groups other than olefins may also be included.

[0032] Examples of vinyl unsaturated carboxylic acids include: (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, iconic acid, citraconic acid, crotonic acid, isocrotonic acid, etc. Examples of their anhydrides include: Nadic acid™ (internal cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, etc.

[0033] Examples of esters of vinyl unsaturated carboxylic acids include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, n-pentyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, acrylic acid, tridecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isoborneol methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dimethylaminoethyl methacrylate, etc. (Meth)acrylates such as diethylaminoethyl acrylate; hydroxyl-containing (meth)acrylates such as hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate; epoxy-containing (meth)acrylates such as glycidyl acrylate and methyl glycidyl acrylate; and aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, N,N-dipropylaminoethyl acrylate, N,N-dibutylaminoethyl acrylate, and N,N-dihydroxyethylaminoethyl acrylate.

[0034] Examples of monomers containing unsaturated vinyl groups other than olefins include: vinyl isocyanates, isopropenyl isocyanates, and other vinyl groups containing isocyanate groups; aromatic vinyl groups such as styrene, α-methylstyrene, vinyltoluene, and tributylstyrene; vinyl groups containing acrylamide groups such as acrylamide, methacrylamide, N-hydroxymethylmethacrylamide, diacetone acrylamide, and maleic acid acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated sulfonic acids such as styrene sulfonic acid, sodium styrene sulfonate, and 2-acrylamide-2-methylpropanesulfonic acid; and unsaturated phosphoric acids such as mono(2-methacryloxyethyl) phosphate and mono(2-acryloxyethyl) phosphate.

[0035] Two or more of these may also be used. Among these, vinyl unsaturated carboxylic anhydrides are preferred, and maleic anhydride is even more preferred.

[0036] Here, to improve the flexural and tensile strength of the molded article, it is preferable to use both unmodified and modified polypropylene resins. Especially from the viewpoint of balancing flame retardancy and mechanical properties, it is preferable to use unmodified polypropylene resin to modified polypropylene resin in a weight ratio of 95 / 5 to 75 / 25. More preferably, it is 95 / 5 to 80 / 20, and even more preferably, it is 90 / 10 to 80 / 20.

[0037] Furthermore, polyamide resins are resins that use amino acids, lactones, or diamines and dicarboxylic acids as main raw materials. Representative examples of such main raw materials include: amino acids such as 6-aminohexanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and p-aminomethylbenzoic acid; lactones such as ε-caprolactam and ω-laurolactam; and tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5- Aliphatic diamines such as methylnonamethylenediamine; aromatic diamines such as m-phenylenedimethyldiamine and p-phenylenedimethyldiamine; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperidine , aminoethylpiperazine Alicyclic diamines, etc.; aliphatic dicarboxylic acids such as adipic acid, octanoic acid, azelaic acid, sebacic acid, and dodecanoic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfonylisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. Two or more of these may also be used.

[0038] In this invention, polyamide resins with a melting point of 200°C or higher are particularly useful from the perspective of excellent heat resistance or strength. Specific examples include: polyhexamethylene hexamethylenediamine (Nylon 6), polyhexamethylene hexamethylenediamine (Nylon 66), polyhexamethylenediamine / polyhexamethylenediamine copolymer (Nylon 6 / 66), polytetramethylene hexamethylenediamine (Nylon 46), polyhexamethylene decanediamine (Nylon 610), polyhexamethylene dodecylamine (Nylon 612), polydecanediamine (Nylon 1010), polydecanediamine (Nylon 1012), polydodecylamine (Nylon 1212), polyundecylamine (Nylon 11), polydodecylamine (Nylon 12), polyhexamethylene terephthalamide / polyhexamethylenediamine copolymer (Nylon 6T / 6), polyhexamethylene hexamethylenediamine / polyhexamethylene terephthalamide copolymer (Nylon 6T / 6), and polyhexamethylenediamine / polyhexamethylene terephthalamide copolymer (Nylon 6T / 6). Nylon 66 / 6T), polyhexamethylene hexamethylenediamine / polyhexamethylene isophthalamide copolymer (Nylon 66 / 6I), polyhexamethylene hexamethylenediamine / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecylamine copolymer (Nylon 6T / 12), polyhexamethylene terephthalamide / poly(2-methylpentamethylene)terephthalamide copolymer (Nylon 6T / M5T), polyisophthalmethylene hexamethylenediamine (Nylon XD6), polynonamethylene terephthalamide (Nylon 9T), and copolymers thereof. Two or more of these may also be used. Among these, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and nylon 9T are preferred.

[0039] There is no particular limitation on the degree of polymerization of these polyamide resins, but it is preferable that the relative viscosity of a solution containing 0.25 g of polyamide resin dissolved in 25 ml of 98% concentrated sulfuric acid, measured at 25°C, is in the range of 1.5 to 5.0, and especially in the range of 2.0 to 3.5.

[0040] Furthermore, the polycarbonate resin is obtained by reacting a diphenol with a carbonate precursor. It can also be a copolymer obtained using two or more diphenols or two or more carbonate precursors. Examples of reaction methods include: interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. This polycarbonate resin is well-known; for example, the polycarbonate resin described in Japanese Patent Application Publication No. 2002-129027 can be used.

[0041] Examples of diphenols include: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)ane (bisphenol A, etc.), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)benzene, etc. Two or more of these can also be used. Among these, bisphenol A is preferred, as it yields polycarbonate resins with superior impact strength. Furthermore, copolymers obtained using bisphenol A with other diphenols exhibit superior heat resistance or low water absorption.

[0042] As carbonate precursors, examples include carbonyl halides, diesters of carbonate, or halocarbamates. Specifically, examples include phosgene, diphenyl carbonate, or dihalocarbamates of diphenols.

[0043] When manufacturing polycarbonate resin from the above-mentioned diphenols and carbonate precursors, catalysts, end-blocking agents, antioxidants that prevent the oxidation of diphenols may also be used as needed.

[0044] Furthermore, the polycarbonate resins of this invention include branched polycarbonate resins copolymerized with trifunctional or higher-functional polyfunctional aromatic compounds, polyester carbonate resins copolymerized with aromatic or aliphatic (including alicyclic) difunctional carboxylic acids, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with both difunctional carboxylic acids and difunctional alcohols. These polycarbonate resins are also well known. Furthermore, two or more of these polycarbonate resins may also be used.

[0045] The molecular weight of the polycarbonate resin is not limited, but the viscosity-average molecular weight is preferably 10,000 to 50,000. If the viscosity-average molecular weight is 10,000 or higher, the strength of the molded article can be further improved. More preferably, it is 15,000 or higher, and even more preferably, it is 18,000 or higher. On the other hand, if the viscosity-average molecular weight is 50,000 or lower, the processability is improved. More preferably, it is 40,000 or lower, and even more preferably, it is 30,000 or lower. When using two or more polycarbonate resins, it is preferable that at least one of them has a viscosity-average molecular weight within the above range. In this case, it is advisable to use a polycarbonate resin with a viscosity-average molecular weight exceeding 50,000 (preferably exceeding 80,000) as the other polycarbonate resin. This polycarbonate resin has high entropy elasticity, which is beneficial in situations such as gas-assisted molding, and it also exhibits characteristics derived from high entropy elasticity (characteristics such as drip prevention, sag characteristics, and improved melt characteristics such as spray modification).

[0046] The viscosity-average molecular weight (M) of polycarbonate resin is obtained by calculating the specific viscosity (ηsp) at 20°C from a solution containing 0.7g of polycarbonate resin dissolved in 100ml of dichloromethane, and then substituting that into the following formula. ηsp / c = [η] + 0.45 × [η]²c (where [η] is the limiting viscosity) [η] = 1.23 × 10⁻⁴ M⁰.⁸³ c=0.7

[0047] In this invention, examples of polyaryl sulfide resins include: polyphenylene sulfide (PPS) resin, polyphenylene sulfide ketone resin, polyphenylene sulfide ketone resin, and random or block copolymers of the like. Two or more of these resins may also be used. Of particular preference is the use of polyphenylene sulfide resin.

[0048] Polyarylene sulfide resins can be manufactured by any method, such as the method for obtaining polymers with relatively small molecular weights as described in Japanese Patent Publication No. 45-3368, the method for obtaining polymers with relatively large molecular weights as described in Japanese Patent Publication No. 52-12240, and the method for obtaining polymers with relatively large molecular weights as described in Japanese Patent Application Publication No. 61-7332.

[0049] The resulting polyarylene sulfide resin can also be subjected to various treatments, including: crosslinking / increasing molecular weight by heating in air; heat treatment under an inert gas environment such as nitrogen or under reduced pressure; washing with organic solvents, hot water, acidic aqueous solutions, etc.; and activation with functionalized compounds such as acid anhydrides, amines, isocyanates, and functionalized disulfide compounds.

[0050] The melt viscosity of the polyarylene sulfide resin is preferably 80 Pa·s or less, and more preferably 20 Pa·s or less, under conditions of 310°C and a shear rate of 1000 / s. There is no particular limitation on the lower limit, but it is preferably 5 Pa·s or more. Two or more polyarylene sulfide resins with different melt viscosities can be used together. Furthermore, the melt viscosity can be measured using a Capillograph apparatus (manufactured by Toyo Seiki Co., Ltd.) under conditions of a die length of 10 mm and a die orifice diameter of 0.5 to 1.0 mm.

[0051] As a polyarylene sulfide resin, it can be used as polyphenylene sulfide resins marketed by Toray Industries, Inc. under the names "Torelina" (registered trademark), DIC Corporation under the names "DIC. PPS" (registered trademark), and Polyplastics Corporation under the names "Durafide" (registered trademark).

[0052] The molding materials of this invention include, for example, fiber-reinforced thermoplastic resin molding material (X) and fiber-reinforced thermoplastic resin molding material (Y). The fiber-reinforced thermoplastic resin molding material (X) is composed of the aforementioned reinforcing fiber (A-1) and thermoplastic resin (B-1), and the reinforcing fiber (A-1) preferably has the same orientation along its length as the fiber-reinforced thermoplastic resin molding material (X). Furthermore, the aforementioned thermoplastic resin (B-1) can be the same as the aforementioned thermoplastic resin (B). Also, from a processability point of view, the length of the fiber-reinforced thermoplastic resin molding material (X) is preferably 3-15 mm, more preferably 5-10 mm. Since long fiber pellets of this length can be made into highly versatile injection molding pellets, the mechanical properties of the molded article can be significantly improved by enhancing flowability and processability during injection molding and by increasing the length of the reinforcing fiber in the molded article.

[0053] Furthermore, the reinforcing fibers (A-1) contained in the fiber-reinforced thermoplastic resin molding material (X) can form a composite in which a compound different from the thermoplastic resin (B) is attached. This composite refers to a composite in which the individual fibers of the reinforcing fibers (A-1) are filled with resin; that is, a composite in which the reinforcing fibers (A-1) are dispersed like islands in a sea of ​​compounds. While it is desirable that the reinforcing fibers (A-1) be completely impregnated by the compound, a certain degree of porosity may also exist in the composite formed by the reinforcing fibers (A-1) and the compound. The porosity of this composite is preferably in the range of 0 to 40%, and more preferably 0 to 20% or less. If the porosity is within this range, the impregnation and fiber dispersion promotion effect is excellent. The porosity is a portion of the composite determined by the ASTM D2734 (1997) test method. Furthermore, there are no particular restrictions on the form of the coating, but examples include a form in which the thermoplastic resin (B) coats part or all of the area surrounding the bundled composite. In this case, it is preferable that the coating covers more than 50% of the area surrounding the bundled composite, more preferably more than 80% of the area surrounding the bundled composite, and most preferably the entire area surrounding the bundled composite is coated with the thermoplastic resin (B). By coating the composite with thermoplastic resin (B), the material properties of the molded material are improved. If the composite and the thermoplastic resin (B) are attached, there are no particular restrictions on the state of the boundary between the composite and the thermoplastic resin (B), but it is preferable that: near the boundary between the composite and the thermoplastic resin (B), the thermoplastic resin (B) partially enters a part of the composite and is miscible with the compounds in the composite; or that it is impregnated with the reinforcing fiber (A-1). In this state, the coated thermoplastic resin (B) is not easily peeled off from the composite, resulting in a molded material with good processability, stable material supply during molding, uniform plasticization, and excellent flowability.

[0054] Figures 1-2 schematically show the shape of the axial cross-section of the molding material of the present invention, and Figures 3-5 schematically show the shape of the orthogonal cross-section of the molding material of the present invention.

[0055] The cross-sectional shape of the molding material is not limited to that shown in the figure, but it is preferred to have a configuration as shown in Figure 1 with a cross-section in the axial direction, in which the reinforcing fiber (A-1)1 is used as the core material and is sandwiched in layers by the thermoplastic resin (B)2.

[0056] Furthermore, as shown in Figures 6 and 8 as perspective oblique views, the reinforcing fiber (A-1) 1 is the core structure, and the thermoplastic resin (B) 2 is the sheath structure. The molding material is preferably configured such that the aforementioned thermoplastic resin (B) covers the core-sheath structure surrounding the reinforcing fiber (A-1). By creating a molding material with such a structure, long bundles of reinforcing fibers can remain in the molded article during molding, thereby improving the mechanical properties of the present invention. Alternatively, a multi-core sheath structure can be configured where a plurality of reinforcing fibers (A-1) are covered with thermoplastic resin (B). In this case, the number of reinforcing fibers (A) is preferably 2 to 6.

[0057] From the perspective of material handling, it is important that the composite and the thermoplastic resin (B) do not separate before molding, and that the thermoplastic resin (B) remains coated on the composite. Since the compound is of low molecular weight, it is mostly a relatively brittle and easily broken solid. Therefore, it is desirable to formulate the thermoplastic resin (B) in a way that protects the composite, preventing the compound from breaking or scattering due to material handling, impacts, or friction during processing before molding.

[0058] The fiber-reinforced thermoplastic resin molding material (Y) is composed of bundled reinforcing fibers (A-2) and thermoplastic resin (B-2). The fiber-reinforced thermoplastic resin molding material (Y) can be pelletized by melt mixing (for example, as shown in Figures 7 and 8, in the form containing bundled reinforcing fibers (A-2) 3). Furthermore, the aforementioned thermoplastic resin (B-1) can be the same as the aforementioned thermoplastic resin (B).

[0059] The aforementioned fiber-reinforced thermoplastic resin molding materials (X) and (Y) can be dry-blended to form a molding material mixture. In this case, the content of reinforcing fiber (A) in the molded product can be easily adjusted. Here, dry blending differs from melt mixing; it refers to stirring and mixing multiple materials at a temperature where the resin components do not melt, resulting in a substantially homogeneous state. This method is primarily suitable for injection molding, extrusion molding, and other applications using pellet-shaped molding materials.

[0060] The molding material of the present invention is preferably a core-sheath structure comprising reinforcing fibers (A-1), bundled reinforcing fibers (A-2), and thermoplastic resin (B). Specifically, it is preferred that the core structure of the aforementioned core-sheath structure comprises reinforcing fibers (A-1), and the reinforcing fibers (A-1) are aligned with the longitudinal direction of the molding material. Furthermore, the sheath structure of the aforementioned core-sheath structure is a fiber-reinforced resin composition (C) comprising bundled reinforcing fibers (A-2) and thermoplastic resin (B). Moreover, the aforementioned reinforcing fibers (A-1) are preferably coated with the aforementioned fiber-reinforced thermoplastic resin composition (C) (e.g., Figure 8).

[0061] In the molding material of the present invention, by creating a state in which the individual fibers of the reinforcing fiber (A-1) are filled with compound (E), the dispersibility of the reinforcing fiber can be improved when the molding material is molded.

[0062] The aforementioned compound (E) preferably has a lower melt viscosity than the thermoplastic resin (B). Because compound (E) has a lower melt viscosity than the thermoplastic resin (B), its flowability is high during molding, which further improves the dispersion of the reinforcing fibers (A-1) within the thermoplastic resin (B). Furthermore, compound (E) preferably has a high affinity for the thermoplastic resin (B). By selecting an impregnation resin with high affinity for the thermoplastic resin (B), it will efficiently and well miscibly combine with the thermoplastic resin (B) during the manufacturing and molding of the molding material, thus further improving the dispersibility of the reinforcing fibers.

[0063] The compound (E) is preferably a resin selected from the group consisting of epoxy resin, phenolic resin, terpene resin and cyclic polyphenylene sulfide. By pre-impregnating the reinforcing fiber (A-1) with the compound (E), the dispersibility of the reinforcing fiber can be improved during the molding of the molding material, and therefore it is more suitable for use.

[0064] The number average molecular weight of compound (E) is preferably 200 to 5000. If the number average molecular weight is 200 or higher, the flexural strength and tensile strength of the molded article can be further improved. The number average molecular weight is more preferably 1000 or higher. Furthermore, if the number average molecular weight is 5000 or lower, the viscosity of the compound is moderately low, thus providing excellent impregnation of the reinforcing fiber (A) and further improving the dispersibility of the reinforcing fiber in the molded article. The number average molecular weight is more preferably 3000 or lower. Moreover, the number average molecular weight of this compound can be determined using gel permeation chromatography (GPC).

[0065] The compound (E) is preferably 0.1 to 20 parts by weight, more preferably 3 to 10 parts by weight, relative to 100 parts by weight of the molding material. By setting it within this range, a molding material with excellent formability and processability can be obtained.

[0066] [Resin Component (D)] In the present invention, the preferred resin component (D) of the bundled reinforcing fiber (A-2) is attached to the surface of the fiber bundle.

[0067] Relative to 100 parts by weight of the bundled reinforcing fiber (A-2), the resin component (D) preferably contains 7 parts by weight or more. When the aforementioned resin component (D) is less than 7 parts by weight, the bundled reinforcing fiber (A-2) has reduced bundle elasticity, which may lead to increased fiber breakage during injection molding, and reduced mechanical properties, therefore it is not advisable. More preferably, it contains 8 parts by weight or more, and even more preferably, 9 parts by weight. There is no upper limit, but it is preferably 20 parts by weight or less, more preferably 17 parts by weight or less, and even more preferably 15 parts by weight or less.

[0068] The aforementioned resin component (D) is preferably a thermosetting resin. By making the resin component (D) a thermosetting resin, the melting of the resin component (D) can be suppressed and the binding properties can be reduced when it is melt-mixed with the thermoplastic resin (B) or (B-2) of the matrix resin, which is therefore more advantageous.

[0069] <Molded Products> The fiber-reinforced resin molded article of the present invention comprises reinforcing fiber (A') and thermoplastic resin (B), and contains 1 to 30 parts by weight of reinforcing fiber (A') and 70 to 99 parts by weight of thermoplastic resin (B) relative to a total of 100 parts by weight of (A') and (B).

[0070] [Reinforcing fibers contained in the molded product] The weight-average fiber length Lw (A') of the reinforcing fiber (A') contained in the molded article is 0.1~2.9 mm, preferably 0.3~2.5 mm, and more preferably 0.5~2.0 mm. By setting the weight-average fiber length of the reinforcing fiber (A') to 0.1 mm or more, the mechanical properties of the molded article can be fully exhibited. On the other hand, by setting the weight-average fiber length of the reinforcing fiber to 2.9 mm or less, the flowability during molding can be improved, and appearance defects of the molded article can be suppressed.

[0071] Here, the "weight-average fiber length" in this invention refers to the weight-average fiber length calculated by applying the method for calculating the weight-average molecular weight, rather than simply obtaining a numerical average. It is calculated using the following formula, taking into account the contribution of fiber length. The following formula is applicable when the fiber diameter and density of the reinforcing fiber (A') are constant. Weight-average fiber length = Σ(Mi²×Ni) / Σ(Mi×Ni) Mi: Fiber length (mm) Ni: Number of reinforcing fibers in fiber length Mi

[0072] The determination of the weight-average fiber length can be performed using the following method. Using an optical microscope equipped with a heat-shrink stage, a test piece is appropriately cut from the molded article. The sample is heated on a heat-shrink stage set at 150–350°C, between glass plates, to create a thin film that is uniformly dispersed. The sample is then observed under an optical microscope (50–200x magnification) while the thermoplastic resin (B) is molten. The fiber lengths of 1000 randomly selected reinforcing fibers (A') are measured, and the weight-average fiber length Lw(A') is calculated using the above formula. Alternatively, the test piece cut from the molded article is immersed in a solvent in which the thermoplastic resin (B) dissolves, and appropriately heated to prepare a solution in which the reinforcing fibers (A') are uniformly dispersed. The solution is then filtered, and the reinforcing fibers (A') dispersed on filter paper are observed under an optical microscope (50–200x magnification). The fiber lengths of 1000 randomly selected reinforcing fibers (A') are measured, and the weight-average fiber length (LwA') is calculated using the above formula. Furthermore, examples of filter paper used at this time include quantitative filter paper (model: No. 5C) manufactured by ADVANTECH.

[0073] There are no particular restrictions on the type of reinforcing fiber (A'), and examples can be found in the description of the reinforcing fiber (A) of the molding material. Furthermore, the preferred type and combination of reinforcing fibers are also the same, and the reasons for their preference are the same.

[0074] Relative to 100 parts by weight of (A) and (B) above, the aforementioned reinforcing fiber (A') is preferably 1 to 30 parts by weight. More preferably, it is 5 to 25 parts by weight. When the reinforcing fiber is less than 1 part by weight, the mechanical properties of the resulting molded article may sometimes be insufficient, and when it exceeds 30 parts by weight, the appearance of the molded article may sometimes become unsatisfactory.

[0075] Furthermore, the reinforcing fiber (A') preferably comprises a bundle of reinforcing fibers (A-2') consisting of 10 or more single yarns with a length of 0.5 to 2.9 mm. The effect of including the bundle of reinforcing fibers (A-2') is the same as that described in the description of the bundle of reinforcing fibers (A-2) in the molding material.

[0076] By setting the weight-average fiber length of the bundled reinforcing fibers (A-2') to 0.5 mm or more, the mechanical properties of the molded article can be fully exhibited. On the other hand, by setting the weight-average fiber length of the bundled reinforcing fibers (A-2') to 2.9 mm or less, the flowability during molding can be improved, and defects in the appearance of the molded article can be suppressed. Preferably, it is 0.3 to 2.5 mm, and even more preferably 0.5 to 2.0 mm.

[0077] The reinforcing fiber (A') in this invention preferably comprises 40% or more of the reinforcing fibers having a fiber length of 0.3 to 1.0 mm. The fiber length ratio of the reinforcing fiber (A') can be calculated by measuring the distribution of 400 reinforcing fibers (A') taken from the molded article. By having a reinforcing fiber ratio of 40% or more of the reinforcing fibers having a fiber length of 0.3 to 1.0 mm, the fiber length of the reinforcing fiber (A') contained in the molded article can be increased, thus resulting in excellent mechanical properties and dimensional stability of the molded article.

[0078] Relative to 100 parts by weight of reinforcing fiber (A'), the molded article of the present invention preferably contains 1 to 50 parts by weight of bundled reinforcing fiber (A-2'). If the content of the aforementioned bundled reinforcing fiber (A-2') is less than 1 part by weight, the mechanical properties and dimensional accuracy of the molded article are poor, and therefore it is not suitable. If the content of the aforementioned bundled reinforcing fiber (A-2') exceeds 50 parts by weight, the mechanical properties are poor, and therefore it is not suitable.

[0079] The molded products of this invention are fiber-reinforced thermoplastic resin molded products with excellent mechanical properties and dimensional accuracy. As molded products made from the molding material of this invention, they are widely used in: electrical and electronic instruments, household appliances, automotive parts, and sports equipment parts. As electrical and electronic instrument parts, they are suitable for applications such as housings, connectors, speakers, microphones, headphones, small motors, and computer-related parts for televisions, video players, DVD players, cameras, and audio equipment. As household appliances, examples include: VTR parts, television parts, electric irons, hair dryers, rice cooker parts, microwave oven parts, audio equipment, audio-visual equipment parts for laser discs (registered trademark), CDs, DVDs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, and word processor parts. Furthermore, as optical instruments and precision machinery-related parts, examples include: office computer parts, telephone parts, fax machine parts, photocopier parts, binoculars, cameras, and clocks. Examples of automotive parts and vehicle-related components include: door damping pads, door pillars, armrest boxes, various motor housings, roof racks, fenders, decorative elements, bumpers, door panels, roof panels, hoods, trunk lids, door mirror support rods, spoilers, hood vent trim panels, wheel covers, wheel covers, front chin guard frames, headlight frames, door handles, door trim strips, tailgate trim panels, and windshield wipers. Furthermore, the components of this invention are also suitable as sporting goods, and can be used in: golf-related products such as golf club heads, clubs, grips, and golf balls; tennis rackets, tennis balls, badminton rackets, their strings, and shuttlecocks; sports body protection products such as masks, helmets, chest protectors, elbow pads, and knee pads for American football, baseball, and softball; shoe-related products such as soles for sports shoes; fishing tackle-related products such as fishing rods, spools, and bait; summer sports-related products such as surfing; winter sports-related products such as skis and snowboards; and other indoor and outdoor sports-related products. [Example]

[0080] The following examples illustrate the invention in more detail, but the invention is not limited to the descriptions of these examples. First, the evaluation methods for various characteristics used in this embodiment will be explained.

[0081] (1) Weight-average fiber length Test pieces cut from the molded articles were immersed in a solvent in which the thermoplastic resin (B) used in the various examples and comparative examples would dissolve, and were appropriately heated to obtain a solution in which the reinforcing fibers (A) were uniformly dispersed. The solution was then filtered using quantitative filter paper (No. 5C) manufactured by ADVANTECH, and the reinforcing fibers (A) dispersed on the filter paper were observed using an optical microscope (50-200x). The fiber lengths of 1,000 randomly selected reinforcing fibers (A) were measured, and the weight-average fiber length (Lw) was calculated using the following formula. Average fiber length = Σ(Mi²×Ni) / Σ(Mi×Ni) Mi: Fiber length (mm) Ni: Number of fibers in fiber length Mi

[0082] (2) Sapele impact strength test of molded articles The parallel portion of the ISO-type dumbbell-shaped test piece obtained in each embodiment and comparative example was cut out, and a sand impact test with a V-shaped notch was carried out using a Tokyo Testing Machine Inc. C1-4-01 testing machine according to ISO179, and the impact strength (kJ / cm2) was calculated.

[0083] (3) Determination of the flexural modulus of the molded article For ISO-type dumbbell-shaped test pieces obtained by injection molding of the material, bending properties were determined according to ISO 178 (1993). A 3-point bending test fixture (indenter radius 5 mm) was used, with the fulcrum distance set to 64 mm, and the bending modulus was determined at a test speed of 2 mm / min. An INSTRON (registered trademark) universal testing machine model 5566 (manufactured by INSTRON Corporation) was used as the testing machine.

[0084] (4) Dimensional evaluation of molded products (evaluation of warpage) For the 80mm×80mm×1mm thick test pieces obtained through the various embodiments and comparative examples, the difference (t2–t1) between the height (t1) of the central portion of the test piece viewed from the side and the height (t2) of the end portion viewed from the side was evaluated. Three measurements were performed on each test piece, and the average value was used for the evaluation of each embodiment and comparative example. The following criteria were used for judgment, with A and B considered acceptable. A: (t2-t1) = less than 3mm B:(t2-t1)=less than 5mm C:(t2-t1)=5mm or more

[0085] (5) Evaluation of liquidity (spiral flow length) Using an injection molding machine and a mold with a width of 10 mm and a diameter of 2 mm, the material was molded under the temperature conditions shown in the examples, an injection speed of 100 mm / sec, and an injection pressure of 80 MPa. The flow length during molding was measured. The flow length is the average value of 20 shots. This average value was used to evaluate each example and comparative example, and the following criteria were used for judgment, with A and B being considered acceptable. A: 100mm or more B: 50mm or more C: Less than 50mm

[0086] Reference Example 1 Production of Reinforcing Fiber (A-1) (Carbon Fiber (A-1)) Continuous carbon fibers with a total of 24,000 yarns, a single fiber diameter of 7 μm, a mass per unit length of 1.6 g / m, a specific gravity of 1.8 g / cm³, and a surface oxygen concentration ratio [O / C] of 0.2 were obtained by spinning, calcining, and surface oxidation of a copolymer mainly composed of polyacrylonitrile. The strand tensile strength of this continuous carbon fiber was 4,880 MPa, and the strand tensile modulus was 225 GPa. Next, a sizing agent stock solution was prepared by dissolving polyglycerol polyoxypropylene ether, a multifunctional compound, in water at a concentration of 2% by weight. The sizing agent was then applied to the carbon fibers by impregnation and dried at 230°C. The resulting carbon fibers had a sizing agent coating weight of 1.0 wt%.

[0087] See Example 2 Production of bundled reinforcing fibers (A-2)-(1) 200g of shredded and graded waste CFRP (CFRP: carbon fiber reinforced plastic) sheets were evenly spread on a metal tray and placed in a 59-liter electric furnace. Nitrogen gas was introduced into the furnace while the processing temperature was maintained at a specific temperature (400°C) for 1 hour. Subsequently, air was introduced into the furnace while the processing temperature was maintained at a specific temperature (300°C) for 1 hour to obtain recycled chopped carbon fiber yarn. The resin composition (D) was measured, revealing that 10 parts by weight of thermosetting resin adhered.

[0088] See Example 3 Production of bundled reinforcing fibers (A-2)-(2) 200g of crushed and graded waste CFRP sheets were evenly spread on a metal tray and placed in a 59-liter electric furnace. Nitrogen gas was introduced into the furnace while the processing temperature was maintained at a specific temperature (500°C) for 2 hours. Subsequently, air was introduced into the furnace while the processing temperature was maintained at a specific temperature (300°C) for 2 hours to obtain recycled chopped carbon fiber yarn. The resin composition (D) was measured, revealing that 5 parts by weight of thermosetting resin adhered.

[0089] See Example 4 Production of polyphenylene sulfide (B-2) In a 20-liter high-pressure reactor equipped with a stirrer, 2383 g (20.0 moles) of 47% sodium hydrosulfide aqueous solution, 848 g (20.4 moles) of sodium hydroxide (96% purity), 3271 g (33 moles) of N-methyl-2-pyrrolidone (NMP), 541 g (6.6 moles) of sodium acetate, and 3000 g of deionized water were added. While purging with nitrogen at atmospheric pressure, the mixture was slowly heated to 225°C over approximately 3 hours. After distilling off 4200 g of water and 80 g of NMP, the reaction vessel was cooled to 150°C. The amount of hydrogen sulfide scattering per mole of sodium hydrosulfide added was 0.018 moles. Next, 2940 g (20 moles) of p-dichlorobenzene (p-DCB) and 2620 g (26.2 moles) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the mixture was stirred at 400 rpm while the temperature was increased to 227°C at a rate of 0.8°C / min, and then increased to 270°C at a rate of 0.6°C / min, and maintained at 270°C for 170 minutes. The mixture was then cooled to 180°C at a rate of 0.4°C / min, and then rapidly cooled to near room temperature. The contents were removed, diluted with 10 liters of NMP, and filtered through an 80-mesh sieve to separate the solvent and solids. The particles were washed several times with 20 liters of warm water, filtered again, and polyphenylene sulfide (B-1) was obtained. This was then dried by hot air at 80°C and then by vacuum drying at 120°C.

[0090] <Bundled reinforcing fibers (A-2)> (carbon fiber (A-2)-(3)) TV14-006 (made by Toray Industries, Inc.) uses carbon fiber “Torayca” cut fiber.

[0091] <Thermoplastic Resin (B)> (B-1) Polycarbonate resin (manufactured by Teijin Chemicals, Ltd., "Panlite" (registered trademark) L-1225L). (B-2) The polyphenylene sulfide resin prepared using Reference Example 4 was used. (B-3) It is made by pelletizing polypropylene resin (PRIME POLYMER, Inc. "Prime Polypro" (registered trademark) J137) and maleic acid modified polypropylene resin (Mitsui Chemicals, Inc. "Admer" (registered trademark) QE840) at a weight ratio of 85 / 15. (B-4) Polyamide 610 resin (Nylon 610 resin "AMILAN" (registered trademark) CM2001) was used.

[0092] <Compound (E)> (E-1) Epoxy resin (Made by Mitsubishi Chemical Co., Ltd., "JER" 828) was used. (E-2) Terpene resin (manufactured by YASUHARA CHEMICAL, Inc., "Clearon M105") was used. (E-3) Terpene phenol resin (manufactured by YASUHARA CHEMICAL, Inc., "YS Polystar N125").

[0093] (Example 1) A long fiber reinforced resin pellet manufacturing device is used, which employs a TEX-30α type twin-screw extruder (screw diameter 30mm, L / D=32) manufactured by Nippon Steel Works, equipped with a coating die for wire resin coating at the front end. The extruder barrel temperature is set to 230°C, and the polycarbonate resin (B-1) described above is supplied from the main hopper and melt-mixed at a screw rotation speed of 200 rpm. The compound (E-1), which is heated and melted at 250°C, is discharged at a rate of 6 parts by mass relative to the total of 100 parts by mass of (A) and (B). Subsequently, (F-1) is discharged, impregnating a fiber bundle composed of carbon fibers (A-1). Then, a fiber bundle of carbon fibers (A-1) containing compound (E-1) is supplied to the die (3mm in diameter) through which the molten polycarbonate resin (B-1) is discharged, continuously arranged such that the polycarbonate resin (B-1) coats the area around the carbon fibers (A-1). At this point, the internal cross-section of the fiber bundle shows at least a portion of the carbon fiber (A-1) in contact with the polycarbonate resin (B-1). After cooling the resulting bundle, it is cut into pellets with a length of 7 mm to obtain fiber-reinforced thermoplastic resin molding material (X). At this point, the traction speed is adjusted so that the carbon fiber (A-1) is 30 parts by mass relative to a total of 100 parts by mass of (A-1) and (B-1). The length of the carbon fiber (A-1) in the resulting fiber-reinforced thermoplastic resin molding material (X) is substantially the same as the pellet length, and the carbon fiber bundles are arranged parallel to the axis of the molding material.

[0094] Next, for another twin-screw extruder (TEX30α manufactured by Nippon Steel), after supplying thermoplastic resin (B-1) to the main hopper, bundled reinforcing fibers (A-2)-(1) are fed into the molten resin from the side feeder, and the screw rotation speed is set to 200 rpm. The strands ejected from the die head are cooled in water and pelletized by cutting them into 3.0 mm lengths using a strand cutter to obtain fiber-reinforced thermoplastic resin molding material (Y-1) pellets. At this time, the amount of bundled reinforcing fibers (A-2)-(2) is adjusted so that the bundled reinforcing fibers (A-2)-(1) is 30 parts by mass relative to a total of 100 parts by mass of (A-2) and (B-1). Similarly, 10 parts by mass of fiber-reinforced thermoplastic resin molding material (Y-2) pellets were obtained relative to a total of 100 parts by mass of (A-2) and (B-1), and 5 parts by mass of fiber-reinforced thermoplastic resin molding material (Y-3) pellets were obtained relative to a total of 100 parts by mass of (A-2) and (B-1).

[0095] The fiber-reinforced thermoplastic resin molding materials (X) and (Y-1) obtained in this way were dry-blended in the proportions shown in Table 1 to form an intermediate raw material mixture. Injection molding was performed using an injection molding machine (J110AD, Nippon Steel Co., Ltd.) under the following conditions: injection time: 2 seconds, back pressure: 5 MPa, holding pressure: 40 MPa, holding time: 10 seconds, barrel temperature: 260°C, and mold temperature: 80°C. ISO-type dumbbell-shaped test pieces and 80mm × 80mm × 1mm thick warpage evaluation test pieces were prepared, and the spiral flow length was measured. The composition ratios of (A-1), (A-2), (B), and compound (E) in Table 1 were adjusted based on the dry-blending ratios. Here, barrel temperature refers to the temperature of the part of the injection molding machine that heats and melts the molding material, and mold temperature refers to the temperature of the mold into which resin is injected to form a specific shape. The obtained test pieces (molded articles) were left to stand for 24 hours in a constant temperature and humidity chamber adjusted to 23°C and 50%RH for characteristic evaluation. The evaluation results obtained by the aforementioned method are summarized and shown in Table 1.

[0096] (Examples 2-5, 11 and 12, Comparative Examples 1-4) Except for setting the ratios of each component as recorded in Tables 1 and 2, the molding material and the molded sheet were obtained in the same manner as in Example 1 above.

[0097] (Example 6) Except that the screw speed of the biaxial extruder was set to 500 rpm when producing the fiber-reinforced thermoplastic resin molding material (Y), the molding material and test pieces were obtained in the same manner as in Example 1 above. The evaluation results are summarized in Table 1.

[0098] (Example 7) Except for changing the composition ratio or the type of resin and compound used as described in Table 1, and setting the barrel temperature to 320°C and the mold temperature to 130°C, molded articles were made in the same manner as in Example 1, and evaluated. The evaluation results are summarized in Table 1.

[0099] (Example 8) Except for changing the composition ratio or the type of resin and compound used as described in Table 1, and setting the barrel temperature to 220°C and the mold temperature to 60°C, molded articles were made in the same manner as in Example 1, and evaluated. The evaluation results are summarized in Table 1.

[0100] (Example 9) Except for changing the composition ratio or the type of resin and compound used as described in Table 1, and setting the barrel temperature to 270°C and the mold temperature to 60°C, molded articles were produced in the same manner as in Example 1, and evaluated. The evaluation results are summarized in Table 1.

[0101] (Example 10) Using a long fiber reinforced resin pellet manufacturing device with a coating die for wire resin coating at the front end of a TEX-30α type twin-screw extruder (screw diameter 30mm, L / D=32) manufactured by Nippon Steel Works, the extruder barrel temperature was set to 230°C. The bundled reinforcing fibers (A-2)-(1) and polycarbonate resin (B-1) shown above were combined and fed from the main hopper. The mixture was melt-kneaded at a screw speed of 200 rpm to form a fiber reinforced resin composition (C-1). The compound (E-1) heated to molten at 250°C was adjusted to be 6 parts by mass relative to the total of 100 parts by mass of (A) and (B). Subsequently, after (E-1) is extruded and impregnated onto a fiber bundle composed of carbon fibers (A-1), a fiber bundle of carbon fibers (A-1) containing compound (E-1) is supplied to the die (3 mm in diameter) through which the molten fiber-reinforcing resin composition (C-1) is extruded, and the fiber bundle is continuously arranged such that the fiber-reinforcing resin composition (C-1) covers the carbon fibers (A-1). At this time, the internal cross-section of the fiber bundle is such that at least a portion of the carbon fibers (A-1) is in contact with the fiber-reinforcing resin composition (C-1). After the resulting bundle is cooled, it is cut into pellets with a length of 7 mm to form composite long fiber pellets. At this time, the amount of bundled reinforcing fiber (A-2)-(1) and the traction speed are adjusted such that, relative to a total of 100 parts by weight of (A-1) and (B-1), carbon fibers (A-1) are 20 parts by weight and (A-2) are 10 parts by weight. The carbon fiber (A-1) of the obtained composite long fiber pellets has a length substantially the same as the pellet length, and the carbon fiber bundles are arranged parallel to the axis of the molding material. Molded articles were then produced in the same manner as in Example 1, and evaluated. The evaluation results are summarized in Table 1.

[0102] Examples 1-6, 11, and 12 demonstrate excellent mechanical properties, dimensional accuracy, and flowability. Examples 7-9 show that even with changes in resin type and compound type, the mechanical properties, dimensional accuracy, and flowability remain excellent. Example 10 shows that even when formed into composite long fiber pellets, the mechanical properties, dimensional accuracy, and flowability remain excellent.

[0103] On the other hand, Comparative Example 1, lacking the bundled reinforcing fiber (A-2), resulted in poor flowability. Comparative Example 2, lacking the reinforcing fiber bundle (A-1), resulted in poor impact strength of the molded article. Comparative Example 3, due to the low amount of resin component (D) attached to the bundled reinforcing fiber bundle (A-2), did not form a bundle in the molded article, resulting in poor mechanical properties and dimensional accuracy. Furthermore, because it was dispersed by single yarn, the fiber contact during injection molding increased, hindering resin flow, thus also resulting in poor flowability. Comparative Example 4, using ordinary chopped strands, did not form a bundle in the molded article, resulting in poor mechanical properties and dimensional accuracy. Furthermore, because it was dispersed by single yarn, the fiber contact during injection molding increased, hindering resin flow, thus also resulting in poor flowability.

[0104] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 raw material Fiber-reinforced thermoplastic resin molding materials (X) weight 67.0 97.0 83.0 50.0 17.0 67.0 67.0 67.0 67.0 - 33 twenty three Fiber-reinforced thermoplastic resin molding materials (Y) type (Y-1) (Y-1) (Y-1) (Y-1) (Y-1) (Y-1) (Y-1) (Y-1) (Y-1) - (Y-2) (Y-3) weight 33.0 3.0 17.0 50.0 83.0 33.0 33.0 33.0 33.0 - 67 77 Reinforced fiber (A-1) type (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) weight 20.0 29.0 25.0 15.0 5.0 20.0 20.0 20.0 20.0 20.0 10 7 Bundle-shaped reinforcing fibers (A-2) type (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) (A-2) -(1) weight 10.0 1.0 5.0 15.0 25.0 10.0 10.0 10.0 10.0 10.0 6.7 3.9 Thermoplastic resin (B) type (B-1) (B-1) (B-1) (B-1) (B-1) (B-1) (B-2) (B-3) (B-4) (B-1) (B-1) (B-1) weight 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 83.3 89.1 Compound (E) type (E-1) (E-1) (E-1) (E-1) (E-1) (E-1) (E-1) (E-2) (E-3) (E-1) (E-1) (E-1) content 6.0 8.7 7.5 4.5 1.3 6.0 6.0 6.0 6.0 6.0 3.0 2.1 Molding materials Reinforcing fiber (A) length mm 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 form - bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle Bundle-shaped reinforcing fibers (A-2) length mm 2.5 2.5 2.5 2.5 0.5 0.5 2.5 2.5 2.5 1.0 2.5 2.5 form - bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle bundle Material morphology (coating / blending) - Blending Blending Blending Blending Blending Blending Blending Blending Blending covered Blending Blending Resin component (D) Adhesion amount weight 10.0 10.0 10.0 10.0 8.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 - - thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting thermosetting Molded products Evaluation results Fiber length LwA' in the molded article mm 1.0 0.7 0.7 1.0 0.6 1.0 1.0 1.0 1.0 0.8 1.1 1.1 Flexural modulus GPa 22.0 25.0 24.0 22.0 19.0 19.0 25.0 17.0 20.0 21.0 14.0 11.0 Notched impact strength of Sapele kJ / m2 15.0 19.0 17.0 12.0 7.0 10.0 10.0 10.0 16.0 13.0 12.0 10.0 Warp - A A A B B B A A A A B B Liquidity - A B B A B A A A A A A A

[0105] [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 raw material Fiber-reinforced thermoplastic resin molding materials (X) weight 100.0 0.0 67.0 67.0 Fiber-reinforced thermoplastic resin molding materials (Y) type (Y-1) (Y-1) (Y-1) (Y-1) weight 0.0 100.0 33.0 33.0 Reinforced fiber (A-1) type (A-1) - (A-1) (A-1) weight 30.0 0.0 20.0 20.0 Bundle-shaped reinforcing fibers (A-2) type - (A-2) -(1) (A-2) -(2) (A-2) -(3) weight 0.0 30.0 10.0 10.0 Thermoplastic resin (B) type (B-1) (B-1) (B-1) (B-1) weight 70.0 70.0 70.0 70.0 Compound (E) type (E-1) (E-1) (E-1) (E-1) content 7.5 0.0 5.0 5.0 Molding materials Reinforcing fiber (A) length mm 7.0 - 7.0 7.0 form - bundle - bundle bundle Bundle-shaped reinforcing fibers (A-2) length mm - 2.5 0.4 0.2 form - - bundle single yarn single yarn Material morphology (coating / blending) - - - Blending Blending Resin component (D) Adhesion amount weight - 8.0 5.0 - - - - thermosetting thermosetting - Molded products Evaluation results Fiber length LwA' in the molded article mm 1.1 - 1.0 0.2 Flexural modulus GPa 23.0 24.0 15.0 15.0 Notched impact strength of Sapele kJ / m2 13.0 5.0 6.0 6.0 Warp - A C C C Liquidity - C A C C

[0106] 1: Reinforced Fiber (A-1) 2: Thermoplastic resin (B) 3: Bundle-shaped reinforcing fibers (A-2)

Claims

1. A fiber-reinforced resin molding material comprising reinforcing fiber (A) and thermoplastic resin (B), wherein, relative to a total of 100 parts by weight of (A) and (B), the fiber-reinforced resin molding material comprises 1 to 30 parts by weight of reinforcing fiber (A) and 70 to 99 parts by weight of thermoplastic resin (B), wherein the reinforcing fiber (A) comprises reinforcing fiber (A-1) and bundled reinforcing fiber (A-2), wherein the reinforcing fiber (A-1) has a length of 3 to 15 mm and is aligned with the longitudinal direction of the molding material, and the length of the reinforcing fiber (A-1) is the same as the length of the molding material in the longitudinal direction, and the bundled reinforcing fiber (A-2) is composed of 10 or more single yarns with a length of 0.5 to 2.9 mm.

2. The fiber-reinforced resin molding material as claimed in claim 1, wherein the aforementioned fiber-reinforced resin molding material comprises fiber-reinforced resin molding material (X) and fiber-reinforced resin molding material (Y), the fiber-reinforced resin molding material (X) comprises reinforcing fiber (A-1) and thermoplastic resin (B-1), the reinforcing fiber (A-1) is aligned with the length direction of the fiber-reinforced resin molding material (X), and the fiber-reinforced resin molding material (Y) comprises bundled reinforcing fiber (A-2) and thermoplastic resin (B-2).

3. The fiber-reinforced resin molding material of claim 1, wherein the fiber-reinforced resin molding material has a core-sheath structure, the core structure of the core-sheath structure includes reinforcing fibers (A-1), and the reinforcing fibers (A-1) are aligned with the length direction of the molding material, the sheath structure of the core-sheath structure is a fiber-reinforced resin composition (C) comprising bundled reinforcing fibers (A-2) and thermoplastic resin (B), and the sheath structure covers the core structure.

4. The fiber-reinforced resin molding material as claimed in claim 1, wherein the aforementioned reinforcing fiber (A-1) and bundled reinforcing fiber (A-2) are both carbon fibers.

5. The fiber-reinforced resin molding material of claim 2, wherein, relative to 100 parts by weight of reinforcing fiber (A), the content of the aforementioned reinforcing fiber (A-1) and bundled reinforcing fiber (A-2) is 50 to 99 parts by weight of reinforcing fiber (A-1) and 1 to 50 parts by weight of bundled reinforcing fiber (A-2).

6. The fiber-reinforced resin molding material of any one of claims 1 to 5, wherein the resin component (D) is attached to the surface of the fiber bundle of the aforementioned bundled reinforcing fibers (A-2).

7. The fiber-reinforced resin molding material of claim 6, wherein the aforementioned resin component (D) is a thermosetting resin, and is contained in 7 or more parts by weight relative to 100 parts by weight of bundled reinforcing fibers (A-2).

8. The fiber-reinforced resin molding material of claim 1, wherein the aforementioned thermoplastic resin (B) comprises at least one selected from polyamide resin, polycarbonate resin, polyphenylene sulfide resin and polypropylene resin.

9. A fiber-reinforced resin molded article comprising reinforcing fiber (A') and thermoplastic resin (B), wherein, relative to a total of 100 parts by weight of (A') and (B), the fiber-reinforced resin molded article comprises 1 to 30 parts by weight of reinforcing fiber (A') and 70 to 99 parts by weight of thermoplastic resin (B), the weight average fiber length Lw (A') of the reinforcing fiber (A') is 0.1 to 2.9 mm, and the reinforcing fiber (A') comprises a bundle of reinforcing fibers (A-2') composed of 10 or more single yarns with a length of 0.5 to 2.9 mm.

10. The fiber-reinforced resin molded article of claim 9, wherein the proportion of the aforementioned reinforcing fibers (A') having a fiber length of 0.3 to 1.0 mm is 40% or more.

11. The fiber-reinforced resin molded article of claim 10, wherein the aforementioned bundled reinforcing fiber (A-2') is contained in 1 to 50 parts by weight relative to 100 parts by weight of reinforcing fiber (A').

12. The fiber-reinforced resin molded article as claimed in claim 9, wherein the aforementioned reinforcing fiber (A') is carbon fiber.

13. A fiber-reinforced resin molded article as claimed in any of claims 9 to 12, wherein the resin component (D) is attached to the surface of the fiber bundle of the aforementioned bundled reinforcing fibers (A-2').

14. The fiber-reinforced resin molded article of claim 13, wherein the aforementioned resin component (D) is a thermosetting resin, and is contained in 7 or more parts by weight relative to 100 parts by weight of bundled reinforcing fibers (A-2').

15. A fiber-reinforced resin molded article as claimed in any one of claims 9 to 12, wherein the aforementioned thermoplastic resin (B) comprises at least one selected from polyamide resin, polycarbonate resin, polyphenylene sulfide resin and polypropylene resin.

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