Fiber-reinforced thermoplastic resin composition

Abstract

This invention relates to a fiber-reinforced thermoplastic resin composition comprising 5 to 50 parts by weight of reinforcing fibers (A) containing at least carbon fibers, 20 to 94.5 parts by weight of thermoplastic resin (B), and 0.5 to 30 parts by weight of rosin resin (C), wherein the rosin resin (C) has an acid value and / or hydroxyl value of 100 mg KOH / g or higher. Because it comprises reinforcing fibers containing at least carbon fibers and the aforementioned specific rosin resin, the fiber-reinforced thermoplastic resin composition of this invention can achieve high reinforcing effect due to the reinforcing fibers, as well as excellent tensile strength, impact strength, and appearance quality, particularly excellent blackness of the molded articles.

Description

Technical Field

[0001] This invention relates to a fiber-reinforced thermoplastic resin composition comprising at least carbon fiber and rosin resin. Prior Technology

[0002] Molded articles containing reinforcing fibers and thermoplastic resins are widely used in sporting goods, aerospace, and general industrial applications due to their lightweight nature and excellent mechanical properties. These reinforcing fibers include metal fibers such as aluminum and stainless steel fibers, inorganic fibers such as silicon carbide fibers and carbon fibers, aramid fibers, and poly(p-phenylene oxide). Organic fibers such as poly-p-phenylene benzoxazole (PBO) fiber are available, but from the perspective of balancing specific strength, specific stiffness and lightweight, carbon fiber is suitable, among which polyacrylonitrile (PAN) carbon fiber is suitable.

[0003] By combining with thermoplastic resins, reinforcing fibers can provide excellent reinforcement. However, to further enhance this effect, the reinforcing fibers must be uniformly dispersed within the thermoplastic resin molded article. When the reinforcing fibers exist in an uneven state, i.e., as fiber bundles, a decrease in tensile strength and impact strength is observed. Therefore, when used as structural components requiring strength, sufficient reinforcement cannot be achieved, and breakage may occur during practical use. Furthermore, an uneven fiber dispersion can sometimes cause defects such as uneven coloring in the appearance of the molded article. Therefore, there is a need for a fiber-reinforced thermoplastic resin composition with excellent tensile strength, impact strength, and excellent appearance quality.

[0004] As a means to improve the mechanical properties and appearance quality of fiber-reinforced thermoplastic resin molded articles, examples include: using a terpene-based resin to combine reinforcing fibers and thermoplastic resin (e.g., Patent Document 1). Furthermore, as a means to improve the reinforcing effect of concrete components, a method of compounding reinforcing fibers with concrete and mortar is proposed (e.g., Patent Document 2). Further, as a means to improve the adhesion of thermoplastic resin, a modified polypropylene resin in which rosin resin is added is proposed (e.g., Patent Document 3). As a means to improve the impact resistance of fiber-reinforced thermoplastic resin molded articles, examples include: using a terpene-based resin to a melt-mixed compound; wherein the melt-mixed compound is composed of reinforcing fibers, thermoplastic resin, and a resin having reactive functional groups (e.g., Patent Document 4). Furthermore, a means to improve impact resistance by using organic fibers in addition to carbon fibers is proposed (e.g., Patent Document 5). However, for molded articles obtained using these technologies, the following issues arise due to insufficient fiber dispersion of the reinforcing fibers in fiber-reinforced thermoplastic resin molded articles: insufficient tensile strength, impact strength, and appearance quality, especially insufficient blackness.

[0005] Therefore, in terms of conventional technology, it is not yet possible to obtain fiber-reinforced thermoplastic resin molded articles with high tensile strength, impact characteristics and good appearance quality in fiber-reinforced thermoplastic resin molded articles with thermoplastic resin as the matrix. It is hoped that such a fiber-reinforced thermoplastic resin composition can be developed. [Previous Technical Documents] [Patent Literature]

[0006] Patent Document 1: Japanese Patent Application Publication No. 10-138379 Patent Document 2: Japanese Patent Application Publication No. 2011-162905 Patent Document 3: Japanese Patent Application Publication No. 2016-74866 Patent Document 4: International Publication No. 2010 / 107022 Patent Document 5: International Publication No. 2014 / 098103 Summary of the Invention

[0007] [The problem the invention aims to solve] In view of the aforementioned problems of the prior art, the object of the present invention is to provide a fiber-reinforced thermoplastic resin composition that can produce fiber-reinforced thermoplastic resin molded articles with excellent tensile strength, impact strength, appearance quality, and especially blackness. [Methods used to solve problems]

[0008] To address the aforementioned issues, the present invention primarily comprises the following components. (1) A fiber-reinforced thermoplastic resin composition comprising: 5 to 50 parts by weight of reinforcing fiber (A) containing at least carbon fiber, 20 to 94.5 parts by weight of thermoplastic resin (B), and 0.5 to 30 parts by weight of rosin resin (C), wherein the rosin resin (C) has an acid value and / or hydroxyl value of 100 mg KOH / g or higher. (2) The fiber-reinforced thermoplastic resin composition as described in (1) contains 1 to 100 parts by weight of rosin resin (C) relative to 100 parts by weight of the aforementioned reinforcing fiber (A). (3) The fiber-reinforced thermoplastic resin composition as described in (1) or (2), wherein the aforementioned rosin resin (C) is modified. (4) The fiber-reinforced thermoplastic resin composition described in any one of (1) to (3), wherein the aforementioned rosin resin (C) comprises at least one selected from the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin ester and rosin polyol. (5) The fiber-reinforced thermoplastic resin composition described in any of (1) to (4) wherein the heat loss of the aforementioned rosin resin (C) at 270°C (hereinafter also referred to as "heat loss") is less than 5%. (6) The fiber-reinforced thermoplastic resin composition described in any one of (1) to (5), wherein the aforementioned reinforcing fiber (A) further comprises at least one selected from the group consisting of organic fibers and glass fibers. (7) The fiber-reinforced thermoplastic resin composition as described in (6), wherein the aforementioned organic fiber is selected from at least one of the group comprising polyamide fiber, polyester fiber, liquid crystal polyester fiber, polyarylate sulfide fiber and fluoropolymer fiber. (8) The fiber-reinforced thermoplastic resin composition described in any of (1) to (7), wherein the weight average fiber length (Lw) of the aforementioned reinforcing fiber (A) is 0.1 to 7.0 mm. (9) The fiber-reinforced thermoplastic resin composition described in any one of (1) to (8), wherein the aforementioned thermoplastic resin (B) comprises at least one selected from the group consisting of polyamide resin, polyolefin resin, polycarbonate resin and polyphenylene sulfide resin. (10) The fiber-reinforced thermoplastic resin composition described in any one of (1) to (9), wherein the aforementioned thermoplastic resin (B) comprises at least two different thermoplastic resins (Ba) and (Bb). (11) The fiber-reinforced thermoplastic resin composition as described in (10) contains 20 to 94.5 parts by weight of a melt-blended resin composition (B1) obtained by melt-blending a thermoplastic resin (Ba) and a thermoplastic resin (Bb), wherein the aforementioned thermoplastic resin (Bb) is a thermoplastic resin having reactive functional groups; the aforementioned melt-blended resin composition (B1) contains: a thermoplastic resin (Ba) and a resin (Bb) having reactive functional groups, and a compound (Bc) generated by the reaction of the resin (Ba) and the resin (Bb), and the aforementioned melt-blended resin composition (B1) is a resin (Bb) having reactive functional groups dispersed in the thermoplastic resin (Ba) in a particulate form with a number average particle size of 10 to 1,000 nm. (12) The fiber-reinforced thermoplastic resin composition as described in (11), wherein the thermoplastic resin (Ba) contained in the aforementioned melt-mixed resin composition (B1) forms a continuous phase, the resin (Bb) having reactive functional groups forms a dispersed phase, and the dispersed phase contains microparticles with a particle size of 1 to 100 nm containing the compound (Bc). (13) The fiber-reinforced thermoplastic resin composition as described in (12) wherein the aforementioned microparticles of the aforementioned compound (Bc) occupy an area ratio of 20% or more in the dispersed phase containing the resin (Bb). (14) The fiber-reinforced thermoplastic resin composition described in any one of (11) to (13), wherein the reactive functional group of the aforementioned resin (Bb) is selected from amine, carboxyl, metal salt of carboxyl, epoxy, acid anhydride and... At least one of the zolylinyl groups. (15) The fiber-reinforced thermoplastic resin composition described in any of (10) to (14), wherein the aforementioned thermoplastic resin (Ba) is a polyamide resin and the resin (Bb) is a polyolefin resin. [Effects of the Invention]

[0009] The fiber-reinforced thermoplastic resin composition of this invention comprises reinforcing fibers containing at least carbon fibers and rosin resin with an acid value and / or hydroxyl value of 100 mg KOH / g or higher. Therefore, it can produce fiber-reinforced thermoplastic resin molded articles with high reinforcing effect due to the reinforcing fibers, excellent tensile strength, impact strength, and appearance quality, especially excellent blackness of the molded articles. The fiber-reinforced thermoplastic resin composition of this invention is extremely useful in electrical / electronic machinery, OA machinery, home appliances, frames, moving parts, and automotive components. Simple Explanation of the Diagram

[0010] Figure 1 is a schematic diagram showing an example of the cross-sectional shape of the fiber bundle in this invention. Figure 2 is a schematic diagram showing an example of a preferred longitudinal section shape of the molding material in this invention. Figure 3 is a schematic diagram showing an example of a preferred cross-sectional shape of the molding material in this invention. Figure 4 is a schematic diagram showing another example of the preferred cross-sectional shape of the molding material in this invention. Implementation

[0011] [The form in which the invention is carried out] The present invention will now be described in detail along with its embodiments. The fiber-reinforced thermoplastic resin composition of the present invention (hereinafter sometimes simply referred to as the "composition") comprises: reinforcing fibers (A) containing at least carbon fibers, thermoplastic resin (B), and rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher.

[0012] Regarding the form of the starting materials, the reinforcing fiber (A) is preferably a continuous bundle of reinforcing fibers, which imparts high mechanical properties to the molded article as a reinforcing material. Thermoplastic resin (B) is a matrix resin with relatively high viscosity, high physical properties such as toughness, and it has the function of firmly holding the reinforcing fiber (A), which contains at least carbon fibers, in the molded article. Rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher uniformly disperses the reinforcing fiber (A) in the thermoplastic resin (B), imparting excellent tensile strength, impact strength, and thus good appearance quality.

[0013] Compared to conventional techniques that improve strength and appearance by adding compatibilizers or terpene resins, rosin resin (C) containing an acid value and / or hydroxyl value of 100 mg KOH / g or higher can significantly improve tensile strength, impact strength and appearance.

[0014] Relative to a total of 100 parts by weight of reinforcing fiber (A), thermoplastic resin (B), and rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, the molded article and composition of the present invention contain 5 to 50 parts by weight of reinforcing fiber (A). If the content of reinforcing fiber (A) is less than 5 parts by weight, the tensile strength and impact strength of the molded article will decrease. The content of reinforcing fiber (A) is preferably 10 parts by weight or more. Furthermore, if the content of reinforcing fiber (A) exceeds 50 parts by weight, the dispersibility of reinforcing fiber (A) in the molded article will decrease, and this will often lead to a decrease in the impact strength and appearance quality of the molded article. The content of reinforcing fiber (A) is preferably 30 parts by weight or less.

[0015] The reinforcing fiber (A) contains at least carbon fiber. Furthermore, there are no particular restrictions on the types of other fibers contained in the reinforcing fiber (A), but glass fiber and organic fiber are suitable for achieving high reinforcing effects. Depending on the desired reinforcing effect, it is preferable to use two or more types of these reinforcing fibers. In this case, the combination of reinforcing fibers should be appropriately selected according to the desired properties.

[0016] In terms of types of carbon fiber, examples include: PAN-based carbon fiber, pitch-based carbon fiber, cellulose-based carbon fiber, vapor-grown carbon fiber, and graphitized fibers of these types. PAN-based carbon fiber uses polyacrylonitrile fiber as a raw material. Pitch-based carbon fiber uses petroleum tar and petroleum pitch as raw materials. Cellulose-based carbon fiber uses viscose rayon, cellulose acetate, etc., as raw materials. Vapor-grown carbon fiber uses hydrocarbons, etc. Among these, PAN-based carbon fiber is superior in terms of its excellent balance between strength and elastic modulus. Furthermore, to further improve conductivity, carbon fibers coated with metals such as nickel, copper, or ytterbium can also be used.

[0017] The surface oxygen concentration ratio [O / C] of carbon fiber is preferably 0.05 to 0.5. The surface oxygen concentration ratio [O / C] is the ratio of the number of oxygen (O) to the number of carbon (C) atoms on the fiber surface, measured by X-ray photoelectron spectroscopy. A surface oxygen concentration ratio of 0.05 or higher ensures sufficient functional groups on the carbon fiber surface and achieves stronger adhesion, thus improving flexural and tensile strength. More preferably, it is 0.08 or higher, and even more preferably, it is 0.1 or higher. Furthermore, there is no particular upper limit to the surface oxygen concentration ratio, but from the perspective of balancing the workability and productivity of carbon fiber, it is generally preferred to be 0.5 or lower. More preferably, it is 0.4 or lower, and even more preferably, it is 0.3 or lower.

[0018] The surface oxygen concentration ratio of carbon fibers was determined by X-ray photoelectron spectroscopy according to the following procedure. First, the sizing agent and other substances adhering to the surface of the carbon fibers were removed using a solvent. The resulting carbon fiber bundle was cut into 20 mm pieces and laid out side by side on a copper sample support. AlKα1,2 was used as the X-ray source, and the sample chamber was maintained at 1×10⁻⁸ Torr. The kinetic energy (KE) of the C1s peak was aligned to 1202 eV as a correction value for the charged associated peak during measurement. A baseline was drawn in the range of 1191–1205 eV (KE) to obtain the C1s peak area. A baseline was drawn in the range of 947–959 eV (KE) to obtain the O1s peak area.

[0019] Here, the so-called surface oxygen concentration ratio is calculated in terms of the atomic ratio from the ratio of the O1s peak area to the C1s peak area using the inherent sensitivity correction value of the device. An International Electric Corporation Model ES-200 was used as the X-ray photoelectron spectroscopy device, and the sensitivity correction value was set to 1.74.

[0020] The means of controlling the surface oxygen concentration ratio [O / C] to be between 0.05 and 0.5 are not particularly limited, but examples include electrolytic oxidation treatment, chemical oxidation treatment and gas phase oxidation treatment, among which electrolytic oxidation treatment is preferred.

[0021] The average fiber diameter of carbon fiber is not particularly limited, but from the viewpoint of the mechanical properties and surface appearance of the molded product, it is preferably 1~20μm, more preferably 3~15μm. Regarding the number of single yarns when forming reinforcing fiber bundles, there is no particular limitation, but it is preferably 100~350,000 yarns, and from a production point of view, it is more preferably 20,000~100,000 yarns.

[0022] For purposes such as improving the adhesion between carbon fibers and the thermoplastic resin (B) of the matrix resin, surface treatment of carbon fibers is acceptable. Examples of surface treatment methods include electrolytic treatment, ozone treatment, and ultraviolet treatment.

[0023] For purposes such as preventing fuzzing of carbon fibers or improving the adhesion between carbon fibers and the thermoplastic resin (B) of the matrix resin, it is acceptable for carbon fibers to be coated with a sizing agent. Specifically, sizing agents can include: epoxy resin, phenolic resin, polyethylene glycol, polyurethane, polyester, emulsifier, or surfactant. Two or more of these can also be used. In the molded material, the sizing agent is applied to the surface of the carbon fibers. The sizing agent is preferably water-soluble or water-dispersible, and preferably an epoxy resin with excellent wettability to carbon fibers. Multifunctional epoxy resins are even more preferred.

[0024] Examples of multifunctional epoxy resins include: bisphenol A type epoxy resins, bisphenol F type epoxy resins, aliphatic epoxy resins, and phenolic varnish-type epoxy resins. Among these, aliphatic epoxy resins are preferred due to their superior adhesion to the matrix resin. Because aliphatic epoxy resins have a flexible skeleton, they easily achieve a high-toughness structure even with high crosslinking density. When present between carbon fibers and the matrix resin, their softness and resistance to peeling further enhance the strength of the molded product. Examples of multifunctional aliphatic epoxy resins, such as diglycidyl ether compounds, include: ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polydimethylol diglycidyl ether. In addition, examples of polyglycidyl ether compounds include: glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ether, arabinol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl tertrol polyglycidyl ether, and polyglycidyl ethers of aliphatic polyols.

[0025] Among the aforementioned aliphatic epoxy resins, aliphatic polyglycidyl ether compounds with numerous highly reactive glycidyl groups are more preferred. Aliphatic polyglycidyl ether compounds offer a good balance of flexibility, crosslinking density, and compatibility with the matrix resin, and can further enhance adhesion. More preferably, these are glycerol polyglycidyl ethers, diglycerol polyglycidyl ethers, polyethylene glycol glycidyl ethers, and polypropylene glycol glycidyl ethers.

[0026] The amount of sizing agent attached relative to 100 parts by weight of carbon fiber is preferably 0.01 parts by weight to 10 parts by weight. If the amount of sizing agent attached is 0.01 parts by weight or more, the adhesion to the thermoplastic resin (B) will be further improved. More preferably, it is 0.05 parts by weight or more, and even more preferably, it is 0.1 parts by weight or more. On the other hand, if the amount of sizing agent attached is 10 parts by weight or less, the physical properties of the thermoplastic resin (B) can be maintained at a higher level. More preferably, it is 5 parts by weight or less, and even more preferably, it is 2 parts by weight or less.

[0027] The method of applying the sizing agent is not particularly limited, and examples include: impregnating carbon fibers with the sizing solution through a roller, contacting carbon fibers with a roller coated with the sizing solution, and spraying the carbon fibers with the sizing solution in a mist form. Furthermore, while both batch and continuous processes are possible, a continuous process that allows for better productivity and smaller deviations is preferred. In this case, it is preferable to control the sizing solution concentration, temperature, and yarn tension to ensure that the effective components of the sizing agent adhere uniformly to the carbon fibers within an appropriate range. Moreover, it is even more preferable to use ultrasound to vibrate the carbon fibers when applying the sizing agent.

[0028] The drying temperature and drying time should be adjusted according to the amount of compound adhering. However, from the perspective of completely removing the solvent used to impart sizing agent, shortening the drying time, preventing the thermal degradation of sizing agent, and preventing the sizing treated carbon fiber from hardening and deteriorating its spreadability, the drying temperature is preferably between 150°C and 350°C, and more preferably between 180°C and 250°C.

[0029] Examples of solvents used to dilute sizing agents include water, methanol, ethanol, dimethylformamide, dimethylacetamide, and acetone. However, from the perspectives of ease of operation and disaster prevention, water is preferred. Therefore, when using compounds that are insoluble or poorly soluble in water as sizing agents, it is preferable to add emulsifiers and surfactants and then disperse them in water before use. Specifically, regarding emulsifiers and surfactants, the following can be used: anionic emulsifiers such as styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers, formalin condensates of naphthalene sulfonate, sodium polyacrylate, etc.; cationic emulsifiers such as polyethyleneimine and polyvinyl imidazoline; nonionic emulsifiers such as nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, and sorbitan ester ethyl oxide adducts. However, nonionic emulsifiers with low interaction are preferred, as they are less likely to hinder the adhesion of multifunctional compounds.

[0030] In addition to the aforementioned carbon fibers, the constituent system of this invention may also contain organic fibers and glass fibers. Inorganic fibers such as carbon fibers are rigid and brittle, making them difficult to entangle and prone to breakage. Therefore, fiber bundles composed solely of inorganic fibers present a problem during the manufacture of molded articles: they easily break or detach from the molded article. Thus, by including soft, non-breakable organic fibers that are easily bent within the molded article, the impact strength of the molded article can be significantly improved. In particular, in addition to the impact strength at room temperature, the impact strength at low temperatures can also be improved.

[0031] In this invention, the content of organic fiber in the composition is preferably 1 to 45 parts by weight relative to 100 parts by weight of reinforcing fiber (A). When the content of organic fiber is less than 1 part by weight, the impact strength of the molded article decreases. The content of organic fiber is preferably 2 parts by weight or more, more preferably 3 parts by weight or more, and even more preferably 4 parts by weight or more. Conversely, when the content of organic fiber exceeds 45 parts by weight, the entanglement of fibers increases, the dispersibility of organic fiber in the molded article decreases, and this often leads to a decrease in the tensile strength, impact strength, and appearance quality of the molded article. The content of organic fiber is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less.

[0032] The tensile elongation at break of the organic fibers used in this invention is preferably 10-50%. If the tensile elongation at break of the organic fibers is 10% or more, the impact strength of the molded article can be further improved. More preferably, it is 15% or more. On the other hand, if the tensile elongation at break of the organic fibers is 50% or less, the fiber strength and rigidity of the molded article can be further improved. More preferably, it is 40% or less.

[0033] The tensile elongation at break (%) of organic fibers can be obtained by the following method. A tensile test is conducted in a standard indoor environment (20°C, 65%RH) with a clamping interval of 250 mm and a tensile speed of 300 mm / min. The length of the fiber at the point of cut is measured (but if cut near the clamp, it is considered a clamp break and deleted from the data). The result is calculated to two decimal places using the following formula, and the second decimal place is rounded. The average value of the data n3 is then determined and defined as the tensile elongation at break in this invention. Elongation at break (%) = [(Length at break (mm) - 250) / 250] × 100

[0034] The optimal single fiber fineness of organic fibers is 0.1~10 dtex.

[0035] Organic fibers can be suitably selected within a range that does not significantly reduce the mechanical properties of the molded article. Examples of fibers obtained by spinning the following resins include: polyolefin resins such as polyethylene and polypropylene; Nylon 6, Nylon 66, polyamide resins such as aromatic polyamide; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; fluoropolymers such as polytetrafluoroethylene, perfluoroethylene / propylene copolymer, and ethylene / tetrafluoroethylene copolymer; liquid crystal polyesters, liquid crystal polymers such as liquid crystal polyester amide; polyetherketone, polyethersulfone, polyarylate, and polyacrylonitrile. Two or more of these can also be used. It is preferable to select the appropriate organic fiber based on its elongation at break or its combination with the thermoplastic resin (B) of the matrix resin. In particular, the melting temperature of the organic fiber is preferably 30°C to 150°C higher than the molding temperature (melt temperature) of the thermoplastic resin (B). Alternatively, organic fibers made from resins that are incompatible with thermoplastic resin (B) are preferred because they remain in a fibrous state within the molded article, thus enhancing the impact strength of the molded article. Examples of organic fibers with high melting temperatures include: polyester fibers, liquid crystal polyester fibers, polyphenylene sulfide fibers, polyamide fibers, or PAN-based fire-resistant yarns that are considered non-melting.

[0036] There are no particular limitations on the type of glass fiber used in this invention, and any known glass fiber can be used. The fiber diameter is not particularly limited, but is preferably 9 to 15 μm. Specific examples of glass fibers include T-120, T-187, and T-187H manufactured by Nippon Electric Glass Co., Ltd.

[0037] In general, various adhesives are applied to glass fibers to improve handleability by suppressing linting or static electricity during use, or to improve adhesion to the substrate thermoplastic resin (B). Glass fibers treated with such adhesives can also be used in this invention. The type of adhesive is selected according to the type of substrate thermoplastic resin (B). Furthermore, the amount of adhesive applied to the glass fiber, based on the overall mass of the glass fiber after adhesive application, is preferably 0.1 to 3.0% by weight in terms of solids. If the amount of adhesive applied is 0.1% by weight or more, the aforementioned handleability and adhesion can be sufficiently improved. On the other hand, if the amount of adhesive applied is 3.0% by weight or less, the impregnation of the thermoplastic resin (B) into the glass fiber can be more effectively promoted.

[0038] Regarding adhesives, examples include: silane-based coupling agents such as aminosilanes, epoxysilanes, and acrylate silanes; polymers or their modifications such as vinyl acetate resins, urethane resins, acrylic resins, polyester resins, polyether resins, phenoxy resins, polyamide resins, epoxy resins, and polyolefin resins; and oligomers including waxes, such as polyolefin waxes. Furthermore, the aforementioned polymers or oligomers are generally used in the form of aqueous dispersions or aqueous solutions. The aqueous dispersion is obtained through water dispersibility caused by a surfactant, while the aqueous solution is obtained through water solubility caused by the neutralization or hydration of carboxyl or amide groups present in the polymer or oligomer backbone. In addition to the components mentioned above, the adhesive system may also include: inorganic salts such as lithium chloride and potassium iodide, or antistatic agents represented by fourth-order ammonium salts such as ammonium chloride type or ammonium ethyl sulfate type, and lubricants represented by surfactants such as aliphatic ester system, aliphatic ether system, aromatic ester system, and aromatic ether system.

[0039] In this invention, when glass fiber is included in the composition, its content is preferably 1 to 45 parts by weight relative to 100 parts by weight of reinforcing fiber (A). When the glass fiber content is less than 1 part by weight, the impact strength of the molded article decreases. The glass fiber content is preferably 2 parts by weight or more, preferably 3 parts by weight or more, and more preferably 4 parts by weight or more. Conversely, when the glass fiber content exceeds 45 parts by weight, the entanglement of the fibers increases, the dispersion of the glass fiber in the molded article decreases, and this often leads to a decrease in the tensile strength, impact strength, and appearance quality of the molded article. The glass fiber content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and more preferably 10 parts by weight or less.

[0040] The composition of the present invention contains 20 to 94.5 parts by weight of thermoplastic resin (B) relative to a total of 100 parts by weight of reinforcing fiber (A), thermoplastic resin (B) and rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or more.

[0041] In this invention, the thermoplastic resin (B) is preferably a thermoplastic resin with a molding temperature (melting temperature) of 200-450°C, and examples include: polyolefin resin, polystyrene resin, polyamide resin, vinyl halide 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, etc., any of which is equivalent to an electrical insulator. Two or more of these resins may also be used.

[0042] Among the aforementioned thermoplastic resins (B), polyolefin resins, polyamide resins, polycarbonate resins, and polyarylether resins that are lightweight and have a good balance of mechanical properties and formability are preferred.

[0043] The term "polyolefin resin" as used herein includes both unmodified and modified polyolefin 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, and 1-dodecene, as well as other α-olefins with 2 to 12 carbon atoms other than propylene. Examples of conjugated and non-conjugated dienes include butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Two or more of these may also be used. Regarding the skeletal structure of unmodified polypropylene resin, examples include: homopolymers of propylene, random or block copolymers of propylene with the aforementioned other monomers, or 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 improving the rigidity of the molded article, homopolymers of propylene are preferred; from the viewpoint of improving the impact strength of the molded article, random or block copolymers of propylene with the aforementioned other monomers are preferred.

[0044] Furthermore, regarding the modified polypropylene resin, acid-modified polypropylene resin is preferred, and more preferably, polypropylene resin having carboxylic acid and / or its salt groups bonded to the polymer chain. The aforementioned acid-modified polypropylene resin can be obtained by various methods, for example, by graft polymerization of polypropylene resin with neutralized or unneutralized monomers having carboxylic acid groups and / or saponified or unsaponified monomers having carboxylic acid ester groups.

[0045] Here, regarding neutralized or unneutralized monomers containing carboxylic acid groups, or saponified or unsaponified monomers containing carboxylic acid ester groups, examples include: vinyl unsaturated carboxylic acids, their anhydrides, and their esterifications. Furthermore, compounds containing unsaturated vinyl groups other than alkenes can also be listed.

[0046] Examples of ethylene-based 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.

[0047] Examples of esters of ethylene-based 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, stearyl methacrylate, tridecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isocamphenyl methacrylate, and dicyclopentanyl methacrylate. (meth)acrylate), dicyclopentenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. (meth)acrylates; hydroxyl-containing (meth)acrylates such as hydroxyl-containing (meth)acrylates such as hydroxyl-containing (meth)acrylates such as hydroxyl-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dipropylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, N,N-dihydroxyethylaminoethyl (meth)acrylate, etc.

[0048] Regarding monomers other than olefins that contain unsaturated vinyl groups, examples include: vinyl groups containing isocyanate such as vinyl isocyanate and isopropylene isocyanate; aromatic vinyl groups such as styrene, α-methylstyrene, vinyltoluene, and tert-butylstyrene; vinyl groups containing acrylamide 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-methylpropane sulfonic acid; and unsaturated phosphoric acids such as mono(2-methacryloxyethyl) phosphate and mono(2-acryloxyethyl) phosphate.

[0049] Two or more of these may also be used. Furthermore, among these, ethylene-based unsaturated carboxylic anhydrides are preferred, and maleic anhydrides are even more preferred.

[0050] Here, in order to improve the flexural and tensile strength of the molded article, it is preferable to use unmodified polypropylene resin and modified polypropylene resin together. In particular, 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.

[0051] Furthermore, polyamide resins are resins that use amino acids, lactones, or diamines and dicarboxylic acids as their main raw materials. Representative examples of their main raw materials include: 6-aminohexanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.; lactones such as ε-caprolactam and ω-laurolactam; tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, etc. Aliphatic diamines such as 5-methylnonamethylenediamine, aromatic diamines such as m-phenylenediamine and p-phenylenediamine, 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, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, and other aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, sodium isophthalate-5-sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid, and other aromatic dicarboxylic acids; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and other alicyclic dicarboxylic acids, etc. Two or more of these may also be used.

[0052] In this invention, polyamide resins with a melting point of 200°C or higher are particularly useful from the perspective of excellent heat resistance and strength. Specific examples include: polyhexamethylene hexamethylene diamine (Nylon 6), polyhexamethylene hexamethylene diamine (Nylon 66), polyhexamethylene hexamethylene diamine copolymer (Nylon 6 / 66), polytetramethylene hexamethylene diamine (Nylon 46), polyhexamethylene decanedialide (Nylon 610), polyhexamethylene dodecylamine (Nylon 612), polydecamethylene decalide (Nylon 1010), polydecamethylene dodecylamine (Nylon 1012), polydodecylamine (Nylon 1212), polyundecylamine (Nylon 11), polydodecylamine (Nylon 12), polyhexamethylene terephthalamide / polyhexamethylene diamine copolymer (Nylon 6T / 6), and polyhexamethylene hexamethylene diamine / polyhexamethylene terephthalamide copolymer. Poly(hexamethylene hexamethylenediamine) / poly(hexamethylene isophthalamide) copolymer (Nylon 66 / 6I), poly(hexamethylene hexamethylenediamine) / poly(hexamethylene terephthalamide) / poly(hexamethylene isophthalamide) copolymer (Nylon 66 / 6T / 6I), poly(hexamethylene terephthalamide) / poly(hexamethylene isophthalamide) copolymer (Nylon 6T / 6I), poly(hexamethylene terephthalamide) / polydodecylamine copolymer (Nylon 6T / 12), poly(hexamethylene terephthalamide) / poly(2-methylpentamethylene)terephthalamide copolymer (Nylon 6T / M5T), poly(hexamethylene diphenylacetamide) (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.

[0053] There are no particular limitations on the degree of polymerization of these polyamine resins, but it is more preferably that the relative viscosity of the solution obtained by dissolving 0.25g of polyamine resin in 25ml of 98% concentrated sulfuric acid at 25°C is preferably in the range of 1.5 to 5.0, and particularly in the range of 2.0 to 3.5.

[0054] Furthermore, polycarbonate resins are obtained by reacting diphenols with carbonate precursors. They can also be copolymers 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. Such polycarbonate resins are known in themselves; for example, the polycarbonate resin described in Japanese Patent Application Publication No. 2002-129027 can be used.

[0055] Examples of diphenols include: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)alkanes (bisphenol A, etc.), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, α,α'-bis(4-hydroxyphenyl)m-diisopropylbenzene, and 9,9-bis(4-hydroxy-3-methylphenyl)benzene. Two or more of these can also be used. Among these, bisphenol A is preferred, as it yields polycarbonate resins with superior impact resistance. Furthermore, copolymers obtained using bisphenol A and other diphenols exhibit excellent heat resistance or low water absorption.

[0056] In terms of carbonate precursors, carbonyl halides, carbonate diesters, or haloformates are used, specifically phosgene, diphenyl carbonate, or dihaloformates of diphenols.

[0057] When manufacturing polycarbonate resin from the aforementioned diphenols and carbonate precursors, catalysts, terminating agents, antioxidants that prevent the oxidation of diphenols may also be used as needed.

[0058] Furthermore, the polycarbonate resin of the present invention includes: a branched polycarbonate resin copolymerized from a trifunctional or higher multifunctional aromatic compound; a polyester polycarbonate resin copolymerized from an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid; a copolymer polycarbonate resin copolymerized from a bifunctional alcohol (including alicyclic); and a polyester polycarbonate resin copolymerized from such bifunctional carboxylic acids and bifunctional alcohols. These polycarbonate resins are also known. Furthermore, two or more of these polycarbonate resins may be used.

[0059] The molecular weight of the polycarbonate resin is not specified, but it is preferably a resin with a viscosity average molecular weight of 10,000 to 50,000. A viscosity average molecular weight of 10,000 or higher can improve the strength of the molded article. More preferably, it is 15,000 or higher, and even more preferably, it is 18,000 or higher. On the other hand, a viscosity average molecular weight of 50,000 or lower improves the processability. 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 preferable to use a polycarbonate resin with a viscosity average molecular weight exceeding 50,000, and preferably exceeding 80,000, as the other polycarbonate resin. Such polycarbonate resins have high entropy elasticity, which is advantageous when used in gas-assisted molding and other processes. In addition, they exhibit properties derived from high entropy elasticity (improved drip-preventing properties, drawdown properties, and improved melting properties such as jetting).

[0060] The viscosity-average molecular weight (M) of polycarbonate resin is obtained by inserting the specific viscosity (ηsp) into the following formula, wherein the specific viscosity (ηsp) is obtained at 20°C from a solution containing 0.7g of polycarbonate resin dissolved in 100ml of dichloromethane. ηsp / c = [η] + 0.45 × [η]²c (where [η] is the limiting viscosity) [η] = 1.23 × 10⁻⁴ M⁰.⁸³ c=0.7

[0061] 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 these. Two or more of these may also be used. Polyphenylene sulfide resin is particularly preferred.

[0062] 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, or the method for obtaining polymers with relatively large molecular weights as described in Japanese Patent Publication No. 52-12240 or Japanese Patent Application Publication No. 61-7332.

[0063] The obtained polyarylene sulfide resin can also be subjected to various treatments, such as crosslinking / increasing molecular weight by heating in air; heat treatment in an inert gas environment such as nitrogen or under reduced pressure; cleaning by organic solvents, hot water, acidic aqueous solutions, etc.; and activation by compounds containing functional groups such as acid anhydrides, amines, isocyanates, and functional disulfides.

[0064] 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 also be used together. Furthermore, the melt viscosity can be measured using a capillary chromatography apparatus (manufactured by Toyo Seiki Co., Ltd.) with a die length of 10 mm and a die orifice diameter of 0.5 to 1.0 mm.

[0065] Polyphenylene sulfide resins marketed under names such as "Torelina" (registered trademark) manufactured by Toray (stock), "DIC.PPS" (registered trademark) manufactured by DIC (stock), and "Durafide" (registered trademark) manufactured by Polyplastics (stock) can also be used as polyaryl sulfide resins.

[0066] The thermoplastic resin composition of the present invention is preferably composed of at least two different thermoplastic resins (Ba) and (Bb).

[0067] The inclusion of both (Ba) and (Bb) in the thermoplastic resin (B) improves the tensile strength and impact strength of the molded article, which is therefore preferable. Furthermore, there are no particular restrictions on the types of thermoplastic resins (Ba) and (Bb) contained in the thermoplastic resin (B). However, for the thermoplastic resin (Ba), it is preferable to use a type of thermoplastic resin as described later, which exhibits excellent mechanical strength. Similarly, for the thermoplastic resin (Bb), it is preferable to use a type of thermoplastic resin as described later, particularly one that exhibits excellent impact resistance. It is also preferable to use two or more of these thermoplastic resins in combination, depending on the desired effect. In this case, the combination of thermoplastic resins should be appropriately selected according to the desired properties.

[0068] Furthermore, the thermoplastic resin (B) in the composition of the present invention may also be a melt-blended resin composition (B1), which is composed of: thermoplastic resin (Ba), a resin having reactive functional groups (Bb), and a compound (Bc) generated by the reaction of (Ba) and (Bb); relative to a total of 100 parts by weight of reinforcing fiber (A), melt-blended resin composition (B1), and rosin resin (C), it contains 20 to 94.5 parts by weight of melt-blended resin composition (B1) obtained by melt-blending thermoplastic resin (Ba) and resin having reactive functional groups (Bb).

[0069] <Thermoplastic resin (Ba)> In this invention, the thermoplastic resin (Ba) preferably has a molding temperature (melt temperature) of 200-450°C, and examples include: polyolefin resin, polystyrene resin, polyamide resin, vinyl halide 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., any of which is equivalent to an electrical insulator. Two or more of these can also be used. From the viewpoints of processability, mechanical properties, and lightweight, polyolefin resin, polyamide resin, polycarbonate resin, and polyphenylene sulfide resin are preferred.

[0070] <Resins with reactive functional groups (Bb)> The resin used as the base for the resin (Bb) having reactive functional groups is not particularly limited, but at least one resin selected from the following and different from the aforementioned polyamide resin (Ba) can be used: polyamide, polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polylactic acid, polyacetal, polyurethane, polytetrafluoroethylene, polyetherimide, polyamideimide, polyimide, polyetherurethane, polyetherketone, polythioetherketone, polyetheretherketone, polyethylene, polypropylene, polystyrene and ABS, styrene-based resins, rubber polymers, polyepoxides, etc. Among these, the resin used as the base for the resin (Bb) is preferably selected from polyolefin resins such as polyethylene resin and polypropylene resin, styrene-based resins, and rubber polymers due to the ease of introducing reactive functional groups; furthermore, from the viewpoint of imparting impact absorption, rubber polymers are more preferred.

[0071] Rubber-like polymers contain polymers with low glass transition temperatures, and are some of the polymers whose molecules are bound together by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc. The optimal glass transition temperature for rubber-like polymers is below 25°C. If the glass transition temperature exceeds 25°C, the impact resistance is poor, and therefore the performance is considered suboptimal.

[0072] Regarding rubbery polymers, the following are preferred examples: random copolymers and block copolymers of polybutadiene, polyisoprene, and styrene-butadiene, hydrides of such block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and other diene rubbers; random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins; ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and other ethylene-unsaturated carboxylic acid copolymers; ethylene-acrylates, ethylene-methacrylates, and other ethylene-unsaturated carboxylic acid ester copolymers. Some unsaturated carboxylic acids are metal salts such as ethylene-acrylic acid-acrylic acid metal salts, ethylene-methacrylic acid-methacrylic acid metal salts, and other ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymers; acrylate-butadiene copolymers, such as butyl acrylate-butadiene copolymers and other acrylic elastic polymers; ethylene-vinyl acetate copolymers and other copolymers of ethylene and fatty acid vinyl esters; ethylene-propylene-ethylene norbornene copolymers, ethylene-propylene-hexadiene copolymers and other ethylene-propylene non-conjugated diene terpolymers; butene-isoprene copolymers, chlorinated polyethylene, polyamide elastomers, polyester elastomers and other thermoplastic elastomers, etc.

[0073] From the viewpoint of obtaining excellent impact strength, it is preferable to use ethylene-unsaturated carboxylic acid ester copolymers, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, and copolymers of ethylene and α-olefins when using thermoplastic resins (Ba).

[0074] Regarding the unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer, (meth)acrylate is preferred. Specific examples of unsaturated carboxylic acid esters include: methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearate (meth)acrylate, etc. Here, "(meth)acrylate" means "acrylic acid or methacrylic acid". While there is no particular limitation on the weight ratio of ethylene to unsaturated carboxylic acid ester in the copolymer, it is preferably in the range of 90 / 10 to 10 / 90, more preferably in the range of 85 / 15 to 15 / 85. The number average molecular weight of the ethylene-unsaturated carboxylic acid ester copolymer is not particularly limited, but from the viewpoint of flowability and mechanical properties, it is preferably in the range of 1,000 to 70,000.

[0075] The reactive functional groups contained in the resin (Bb) are not particularly limited as long as they are functional groups present in the thermoplastic resin (Ba), but are preferably at least one selected from the following: amine group, carboxyl group, metal salt of carboxyl group, hydroxyl group, epoxy group, acid anhydride group, isocyanate group, mercapto group, etc. Azoline group, sulfonic acid group, etc. Among them, those composed of amino group, carboxyl group, metal salts of carboxyl group, epoxy group, acid anhydride group, and... The groups selected from the zolyl group are more suitable for use due to their high reactivity and fewer side reactions such as decomposition and cross-linking.

[0076] When introducing anhydride groups into rubber polymers, known techniques can be used, and there are no particular limitations. For example, the following methods can be used: copolymerizing anhydrides such as maleic anhydride, isocrine anhydride, norbornene anhydride, citrine anhydride, and 1-butene-3,4-dicarboxylic anhydride with monomers of rubber polymer raw materials, or grafting anhydrides onto rubber polymers.

[0077] Furthermore, when introducing epoxy groups into rubber polymers, known techniques can be used without particular limitations, but the following methods can be used, for example: copolymerizing epoxy-containing vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethyl acrylate, and glycidyl isocyanate with monomers of rubber polymer raw materials; polymerizing rubber polymers using epoxy-containing polymerization initiators or chain transfer agents; and grafting epoxy compounds onto rubber polymers, etc.

[0078] In addition, when When introducing azoline groups into rubbery polymers, the method can be carried out using known techniques without particular limitations, but for example, the following method can be used: introducing 2-isopropenyl- Azoline, 2-vinyl- Azoline, 2-Acryl- Azoline, 2-Styrene- Azoline and other substances have Methods for copolymerizing zoline-based vinyl monomers with monomers of rubber polymer raw materials, etc.

[0079] In resins (Bb) with reactive functional groups, there is no particular limitation on the number of functional groups per molecular chain, but it is usually preferred to have 1 to 10, and preferably 1 to 5 in order to reduce side reactions such as cross-linking.

[0080] In this invention, the melt-blended resin composition (B1) comprises: a thermoplastic resin (Ba), a resin (Bb) having reactive functional groups, and a compound (Bc) generated by the reaction of (Ba) and (Bb). The melt-blended resin composition (B1) can be obtained by melt-blending the thermoplastic resin (Ba) and the resin (Bb) having reactive functional groups. Furthermore, because the resin (Bb) has reactive functional groups, (Bc) is generated by the reaction of (Ba) and (Bb) during melt-blending. The melt-blended resin composition (B1) can be obtained in the form of a thermoplastic resin composition in which the thermoplastic resin (Ba) forms a matrix phase as a continuous layer, and the resin (Bb) is dispersed in particles as a dispersed phase. The structure of the particles containing the resin (Bb) is highly controlled, which greatly contributes to improved impact resistance. For a melt-mixed resin composition (B1) in which thermoplastic resin (Ba) and resin (Bb) are mixed to form a matrix resin and resin (Bb) particles are dispersed in the matrix resin, the number-average particle size of the resin (Bb) particles contained in the melt-mixed resin composition (B1) must be 10 to 1,000 nm. When the number-average particle size is less than 10 nm, the impact resistance characteristic of the present invention is not exhibited; if it exceeds 1,000 nm, the rigidity characteristic of the present invention is reduced, which is undesirable. By achieving improved impact resistance with a small number of resin (Bb) particles whose structure is highly controlled, a fiber-reinforced thermoplastic resin composition molded article with an excellent balance of rigidity and impact resistance can be obtained.

[0081] Furthermore, the fiber-reinforced thermoplastic resin composition molded article of the present invention preferably contains microparticles of a compound (Bc) with an average particle size of 1 to 100 nm, generated by the reaction of thermoplastic resin (Ba) and resin (Bb) in the resin (Bb) particles. Furthermore, the area ratio occupied by the compound (Bc) generated by the reaction of the aforementioned components (Ba) and (Bb) in the resin (Bb) particles is preferably 20% or more. By controlling the structure within the dispersed phase as described above, even if the amount of resin (Bb) forming the dispersed phase is small, a fiber-reinforced thermoplastic resin composition molded article with an excellent balance of rigidity and impact resistance can be obtained.

[0082] Furthermore, morphological observation methods can utilize known techniques. For example, the following method can be used: The cross-section of the test specimen is cut into 1-2 mm squares at its center, and ruthenium tetroxide is used to stain a resin (B2) with reactive functional groups. Then, an ultrathin section (less than 0.1 μm thick, approximately 80 nm) is obtained using an ultramicrotome. A transmission electron microscope is then used to observe the resin portion (excluding the reinforcing fibers) of this section, which contains thermoplastic resin (Ba), resin (Bb), and compounds (Bc). The number-average particle size (Xn) is calculated by randomly selecting more than 400 particles from the acquired image, analyzing the particle size distribution using Scion Corporation's image analysis software "Scion Image," and obtaining the value using the following formula. Number average particle size (Xn) = Σ(Xi×ni) / Σni Xi: Particle size ni: Number of particles conforming to particle size (Xi) (i=1, 2, 3, ..., n)

[0083] The number-average particle size of the resin (Bb) particles can be determined from an image magnified 10,000 times. Furthermore, the number-average particle size of the compound (Bc) formed by the reaction of thermoplastic resin (Ba) and (Bb) contained in the (Bb) particles can be determined from an image magnified 35,000 times.

[0084] The area ratio occupied by compound (Bc) in the resin-containing (Bb) particles was determined using a transmission electron microscope. The image was magnified to 35,000 times, and the area occupied by resin (Bb) and compound (Bc) was analyzed separately using the image analysis software "Scion Image" manufactured by Scion Corporation. The results were obtained by the following formula. Sn = Sp / (Sa² + Sp) Sn: The area ratio (Sn) occupied by compound (Bc) in particles containing resin (Bb). Sa2: Area occupied by resin (Bb) Sp: The area occupied by compound (Bc).

[0085] In this invention, there are no particular limitations on the method of manufacturing the melt-blended resin composition (B1), but the following methods are effective, for example.

[0086] One method for manufacturing melt-mixed resin composition (B1) is as follows: A thermoplastic resin (Ba) and a resin (Bb) with reactive functional groups are fed into a twin-screw extruder. The maximum resin pressure in the kneading zone of the screw is defined as Pkmax (MPa), and the minimum resin pressure in the full flight zone of the screw is defined as Pfmin (MPa). Melt mixing is then performed to satisfy the condition Pkmax ≥ Pfmin + 0.3. The twin-screw extruder has a screw length L to screw diameter D0 ratio of L / D0 of 50 or more and has multiple full flight zones and kneading zones.

[0087] From the perspective of improving mixability and reactivity, an L / D0 value of 60-200 is preferable, with 80-200 being even better. Furthermore, when using a twin-screw extruder with an L / D0 below 50, it is preferable to perform multiple mixing processes to achieve a calculated L / D0 value of 50 or higher for the resin composition. L / D0 is the value calculated by dividing the screw length L by the screw diameter D0. Here, the screw length refers to the length from the upstream end of the screw section to the front end of the screw, where the upstream end is located at the feed port where the thermoplastic resin (Ba) and the resin with reactive functional groups (Bb) are supplied to the screw base. The screw of a twin-screw extruder is composed of screw sections with different lengths and shapes, such as full-flight and kneading disks. In extruders, the side supplying raw materials is sometimes referred to as upstream, and the side expelling molten resin is referred to as downstream.

[0088] When using a twin-screw extruder with an L / D0 of 50 or higher to manufacture melt-mixed resin composition (B1), from the perspective of improving compatibility and reactivity, the screw of the twin-screw extruder preferably has multiple full-threaded zones and kneading zones. The full-threaded zone consists of one or more full threads, while the kneading zone consists of one or more kneading discs.

[0089] If, among the resin pressures displayed by resin pressure gauges located in multiple kneading zones, the resin pressure in the largest kneading zone is defined as Pkmax (MPa), and among the resin pressures displayed by resin pressure gauges located in multiple threaded zones, the resin pressure in the smallest threaded zone is defined as Pfmin (MPa), then it is preferable to manufacture the product with a Pkmax value of (Pfmin+0.3) or higher, and more preferably with a Pkmax value of (Pfmin+0.5) or higher.

[0090] A kneading zone consisting of one or more kneading discs exhibits better mixability and reactivity of the molten resin than a fully threaded zone consisting of one or more fully threaded discs. By filling the kneading zone with molten resin, mixability and reactivity are dramatically improved. Resin pressure is an indicator of the degree of filling; a standard is that higher resin pressure indicates greater filling. In other words, when using a twin-screw extruder, increasing the resin pressure in the kneading zone to a level significantly higher than that in the fully threaded zone effectively promotes the reaction.

[0091] There are no particular limitations on the method for increasing resin pressure in the kneading zone, but the following methods are preferred: introducing a reverse screw zone that has the effect of pushing molten resin back to the upstream side between kneading zones or on the downstream side of the kneading zone, or introducing a sealing ring zone that has the effect of accumulating molten resin, etc. The reverse screw zone and the sealing ring zone include one or more reverse screws or one or more sealing rings, and these can also be combined.

[0092] For example, when a reverse screw zone is introduced between kneading zones or downstream of the kneading zone, if the length of the reverse screw zone is defined as Lr, then from the viewpoint of mixing and reactivity, the reverse screw zone preferably has a length of Lr / D0 = 0.1 to 10. The length Lr / D0 of the reverse screw zone is more preferably 0.2 to 8, and even more preferably 0.3 to 6. When multiple reverse screw zones are provided, it is preferable that each reverse screw zone satisfies the above-mentioned range of Lr / D0. Furthermore, the length Lr of the reverse screw zone is defined as the distance between the following perpendicular lines: the perpendicular line from the upstream end of the upstream reverse screw constituting the reverse screw zone toward the screw shaft centerline, and the perpendicular line from the downstream end of the downstream reverse screw constituting the reverse screw zone toward the screw shaft centerline.

[0093] When manufacturing melt-mixed resin composition (B1) using a twin-screw extruder with an L / D0 of 50 or higher, the extrusion rate is preferably 0.01 kg / h or higher per screw rpm, more preferably 0.05 kg / h to 1 kg / h, further preferably 0.08 to 0.5 kg / h, and most preferably 0.1 to 0.3 kg / h. Here, extrusion rate refers to the weight (kg) of melt-mixed compound ejected from the extruder per hour.

[0094] Furthermore, the preferred numerical range related to extrusion volume in the aforementioned biaxial extruder is based on the extrusion volume of a biaxial extruder with a screw diameter of 41 mm. When the screw diameter varies significantly, for example, when using a biaxial extruder with a diameter less than 30 mm or a diameter greater than 50 mm, the extrusion volume can be replaced and interpreted as follows: relative to the ratio of the screw diameter before and after proportional reduction or enlargement, the extrusion volume preferably follows the 2.5 power law or the 3 power law, and more preferably follows the 2.5 power law, decreasing or increasing accordingly.

[0095] For example, when using a twin-screw extruder with a screw diameter of 20 mm, if the extrusion rate is set according to the 2.5 power law of the screw diameter ratio before and after proportional reduction, then the extrusion rate of the melt compound per 1 rpm is preferably 0.0017 kg / h or more, more preferably 0.0083~0.17 kg / h, further preferably 0.013~0.083 kg / h, and most preferably 0.017~0.050 kg / h.

[0096] Furthermore, when using a twin-screw extruder with a screw diameter of 100 mm, if the extrusion rate is set according to the 2.5 power law of the screw diameter ratio before and after scaling up, then the extrusion rate of the melt compound per 1 rpm of screw is preferably 0.093 kg / h or more, more preferably 0.46~9.29 kg / h, further preferably 0.74~4.65 kg / h, and most preferably 0.93~2.79 kg / h.

[0097] In addition, there are no particular restrictions on the rotational speed of the screw, but it is preferably 10 rpm or more, more preferably 15 rpm or more, and even more preferably 20 rpm or more.

[0098] The residence time in the twin-screw extruder is preferably 1 to 30 minutes, more preferably 1.5 to 25 minutes. This residence time represents the average residence time from the time the raw material is fed into the twin-screw extruder until it is ejected. The residence time is defined as the time from the point at which approximately 1 g of colorant is added along with the raw material at the screw root position of the feedstock, when the uncolored melt blend has been adjusted to a constant melt blending state at a specified extrusion rate, until the extruded material is extruded from the extruder outlet and the color intensity caused by the colorant reaches its maximum.

[0099] When using a twin-screw extruder with an L / D0 of 50 or higher to manufacture melt-mixed resin composition (B1), there are no particular restrictions on the screw of the twin-screw extruder; fully engaged, partially engaged, and non-engaged screws can be used. From the viewpoint of mixing and reactivity, a fully engaged screw is preferred. Furthermore, regarding the direction of screw rotation, both the same direction and opposite directions are acceptable, but from the viewpoint of mixing and reactivity, the same-direction rotation is preferred. Ideally, the screw should be a fully engaged type rotating in the same direction.

[0100] Regarding the screw configuration of the twin-screw extruder, it is used in combination with a full screw thread and / or kneading discs, but preferably it is a screw configuration that effectively imparts a shear field to the molten resin composition. Therefore, as mentioned above, the screw of the twin-screw extruder preferably has multiple kneading zones consisting of one or more kneading discs along its long side. The total length of these kneading zones is preferably 5% to 50% of the total length of the screw, more preferably 10% to 40%, and even more preferably 15% to 30%.

[0101] From the viewpoint of mixing and reactivity, if the length of each kneading zone in the screw of a twin-screw extruder is defined as Lk, then preferably all kneading zones have a length of Lk / D0 = 0.2 to 10. The length Lk / D0 of each kneading zone is more preferably 0.3 to 9, and even more preferably 0.5 to 8. Furthermore, the length Lk of the kneading zone is defined as the distance between the following perpendicular lines: a perpendicular line from the upstream end of the upstream kneading disc constituting the kneading zone towards the screw axis centerline, and a perpendicular line from the downstream end of the downstream kneading disc constituting the kneading zone towards the screw axis centerline. Furthermore, the kneading zones of the twin-screw extruder are preferably not unevenly distributed at specific locations within the screw, but rather configured across the entire region.

[0102] To remove reaction byproducts or thermally degraded substances, it is preferable to set up an exhaust vacuum zone and reduce the pressure to below -0.07 MPa for melt mixing, more preferably to below -0.08 MPa. Here, "gauge pressure" refers to the pressure when atmospheric pressure is set to zero; a lower pressure indicates a higher vacuum and a greater ability to remove volatile components. When the gauge pressure in the exhaust vacuum zone exceeds -0.07 MPa, i.e., the vacuum level is low, the aforementioned volatile components cannot be sufficiently removed, leaving impurities in the polyamide resin composition (B), which is undesirable. By sufficiently removing volatile components in the exhaust vacuum zone, the amount of impurities in the melt-mixed compound can be reduced. There is no particular limitation on the number of exhaust vacuum zones, but it is preferable to set up one or more. Furthermore, there are no particular restrictions on the location of the exhaust vacuum zone, but it is preferable to set at least one zone from the sampling point to the position in front of L / D0=0~10 to effectively remove the aforementioned volatile components.

[0103] The maximum resin temperature is preferably controlled between 180°C and 330°C for melt mixing, and more preferably between 200°C and 325°C. The maximum resin temperature referred to here is the highest temperature measured by resin thermometers evenly distributed at multiple points on the extruder. When the maximum resin temperature is below 180°C, the reactivity between polymers is low, while when it exceeds 330°C, thermal decomposition of the polymer will occur.

[0104] When using a twin-screw extruder, to suppress thermal degradation, it is preferable to introduce an inert gas from the feed section for melt mixing. Nitrogen is preferred as the inert gas.

[0105] Regarding a second method for manufacturing the melt-blended resin composition (B1), one example is a method in which a thermoplastic resin (Ba) and a resin (Bb) having reactive functional groups are subjected to elongation flow while simultaneously being melt-blended. In elongation flow blending, the dispersion efficiency is higher compared to the shear mobility typically used in melt blending, thus the reaction proceeds efficiently, especially in alloying processes accompanied by reactions such as reactive processing.

[0106] When manufacturing a melt-mixed resin composition (B1) by simultaneously elongating and melting the resin, it is preferable to use a melt-mixing process employing an extruder. Examples of extruders include single-screw extruders, twin-screw extruders, and multi-screw extruders with three or more shafts. Among these, single-screw extruders and twin-screw extruders are preferred, with twin-screw extruders being particularly desirable. Furthermore, there are no particular restrictions on the screw of such a twin-screw extruder; fully engaged, partially engaged, and non-engaged screws can be used. From the viewpoint of mixing and reactivity, a fully engaged screw is preferred. In addition, regarding the direction of screw rotation, both the same direction and opposite directions are acceptable, but from the viewpoint of mixing and reactivity, rotating in the same direction is preferred. The optimal screw is a fully engaged type rotating in the same direction.

[0107] In order to provide a suitable elongation flow field for reactive processing, the ratio of the total length of the elongation flow zone to the total length of the extruder screw is preferably in the range of 5% to 60%, more preferably in the range of 10% to 55%, and even more preferably in the range of 15% to 50%.

[0108] In the screw of an extruder, if the length of the elongation flow zone is defined as Lk and the screw diameter as D0, then from the viewpoint of mixing and reactivity, Lk / D0 is preferably 0.2 to 10. More preferably, it is 0.3 to 9, and even more preferably, it is 0.5 to 8. When multiple elongation flow zones are provided, it is preferable that each elongation flow zone satisfies the above-mentioned range of Lk / D0. Furthermore, in this invention, the elongation flow zones are preferably not unevenly distributed at specific locations within the screw, but rather configured across the entire region.

[0109] Regarding the screw configuration for extending the flow zone, the following are preferred examples: a twist kneading disk, which is composed of a kneading disk, wherein the angle formed by the top of the front end side and the top of the rear end side of the kneading disk, i.e., the helical angle θ, is within the range of 0° < θ < 90° in the half-rotation direction of the screw; a threaded screw, wherein a resin passage is formed in the threaded portion of the threaded screw, wherein the cross-sectional area decreases from the front end side to the rear end side of the screw; or a resin passage, which temporarily reduces the cross-sectional area through which the molten resin passes in the extruder.

[0110] The extrusion rate relative to 1 rpm of screw speed is preferably 0.01 kg / h or more. Extrusion rate refers to the weight (kg) of molten compound extruded per hour from the extruder. If the extrusion rate relative to 1 rpm of screw speed is less than 0.01 kg / h, the extrusion rate relative to the screw speed is insufficient, resulting in excessively long residence time in the extruder, leading to thermal degradation. Simultaneously, the resin filling rate in the extruder becomes very low, resulting in inadequate mixing. Furthermore, there are no particular limitations on the screw rotation speed, but it is preferably 10 rpm or more, more preferably 50 rpm or more, and even more preferably 80 rpm or more. Additionally, the extrusion rate is preferably 0.1 kg / h or more, more preferably 0.15 kg / h or more, and even more preferably 0.2 kg / h or more.

[0111] The preferred residence time in the extruder is 1 to 30 minutes, more preferably 1.5 to 28 minutes, and even more preferably 2 to 25 minutes. Residence time refers to the average residence time from the time the raw material is fed into the extruder until it is extruded. The residence time is defined as the time from when approximately 1g of colorant is added along with the raw material at the root of the screw, after the uncolored resin composition has been adjusted to a constant melt-mixed state at a specified extrusion rate, until the extruded material is extruded from the outlet of the extruder and the color intensity caused by the colorant reaches its maximum. When the residence time is less than 1 minute, the reaction time in the extruder is short, and the reaction is not sufficiently promoted, which is undesirable. When the residence time is longer than 30 minutes, the resin will undergo thermal degradation due to the long residence time, which is also undesirable.

[0112] When a twin-screw extruder with an L / D0 of 50 or higher is used to manufacture a melt-mixed resin composition (B1), and when the melt-mixed resin composition (B1) is manufactured by performing elongation flow and melt mixing simultaneously, in either case, the blending ratio of thermoplastic resin (Ba) and resin with reactive functional groups (Bb) is 80-60% by weight of thermoplastic resin (Ba) and 20-40% by weight of resin (Bb). If this is the case, since thermoplastic resin (Ba) forms a continuous phase and resin (Bb) forms a dispersed phase, and the particles containing resin (Bb) contain a compound (Bc) of 1-100 nm formed by the reaction of (Ba) and (Bb), it is preferable that the area ratio occupied by the compound (Bc) is more than 20%.

[0113] The composition of this invention, in addition to the reinforcing fiber (A) and the thermoplastic resin (B), also contains rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher. The rosin resin (C) is not particularly limited, and various known rosin resins can be used. The aforementioned rosin resins can be exemplified by, for example: refined rosin (gum rosin, tall-oil rosin, wood rosin) obtained by refining natural rosin (gum rosin, tall-oil rosin, wood rosin) derived from Pinus massoniana, Pinus slashii, Pinus kesiya, Pinus tunguska, and Pinus palustris, etc., using vacuum distillation, steam distillation, extraction, recrystallization, etc. (hereinafter, natural rosin and refined rosin are collectively referred to as unmodified rosin); hydrogenated rosin obtained by hydrogenating the aforementioned unmodified rosin; disproportionated rosin obtained by disproportionating the aforementioned unmodified rosin; polymerized rosin obtained by polymerizing the aforementioned unmodified rosin; acrylated rosin; maleated rosin; and fumarated rosin. Acid-modified rosin, esterified rosin (hereinafter referred to as rosin esters), rosin phenol resin, rosin polyol, etc. The above-mentioned rosin resins can be used alone or in combination of two or more.

[0114] The rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher is selected from at least one of the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin esters and rosin polyols.

[0115] By setting the acid value and / or hydroxyl value of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, the dispersibility of fibers in fiber-reinforcing resins can be further improved, resulting in excellent mechanical strength and enhanced appearance quality of molded articles, particularly improving blackness. More preferably, it is 120 mg KOH / g; even more preferably, 130 mg KOH / g; and most preferably, 150 mg KOH / g or higher.

[0116] Furthermore, the acid value and / or hydroxyl value of the aforementioned rosin resin is preferably below 300 mg KOH / g. By setting the acid value and / or hydroxyl value to below 300 mg KOH / g, the modification of the thermoplastic resin (B) of the matrix resin can be suppressed, and the decrease in tensile strength and impact strength can be suppressed. Preferably, it is below 270 mg KOH / g, more preferably below 260 mg KOH / g, and even more preferably below 250 mg KOH / g.

[0117] Furthermore, in this invention, the hydroxyl value and acid value are measured using JIS K 0070.

[0118] The rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, from the viewpoint of having excellent mechanical strength among fiber-reinforcing resins, is preferably selected from at least one of the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin esters and rosin polyols, and particularly preferably selected from at least one of the group consisting of acid-modified rosin or rosin polyols.

[0119] The following describes acid-modified rosin, unmodified rosin esters, hydrogenated rosin esters, disproportionated rosin esters, polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, rosin phenol resins, and rosin polyols.

[0120] (Acid-modified rosin) Acid-modified rosin is obtained by adding α,β-unsaturated carboxylic acids to the aforementioned unmodified rosin or disproportionated rosin. Regarding the aforementioned α,β-unsaturated carboxylic acids, there is no particular limitation, and various known α,β-unsaturated carboxylic acids can be used. Specifically, examples include: acrylic acid, methacrylic acid, maleic acid, fumaric acid, icosinic acid, citrate, mucosic acid, maleic anhydride, icosinic anhydride, citrate anhydride, and mucosic anhydride. Among these, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferred. From the perspective of excellent emulsification, the amount of α,β-unsaturated carboxylic acid used is typically about 1 to 20 parts by mass relative to 100 parts by mass of the aforementioned unmodified rosin, preferably about 1 to 3 parts by mass. The aforementioned α,β-unsaturated carboxylic acids can be used alone, or two or more can be used in combination. The method for manufacturing rosin modified with α,β-unsaturated carboxylic acid is not particularly limited, but examples include: adding the α,β-unsaturated carboxylic acid to the unmodified rosin or disproportionated rosin that has been melted under heat, and reacting it at a temperature of about 180°C to 240°C for about 1 to 9 hours. Alternatively, the reaction can be carried out in a closed reaction system while an inert gas such as nitrogen is introduced.

[0121] Furthermore, in the above reaction, known catalysts can also be used, such as Lewis acids like zinc chloride, ferric chloride, and tin chloride, or Brinzyl acids like p-toluenesulfonic acid and methanesulfonic acid. The amount of such catalyst used is typically around 0.01% to 10% by mass relative to the unmodified rosin. In addition, for the α,β-unsaturated carboxylic acid modified rosin described above, rosin modified with α,β-unsaturated carboxylic acids can also be used, which are obtained by further hydrogenation of the α,β-unsaturated carboxylic acid modified rosin as described later. The α,β-unsaturated carboxylic acid modified rosin may also contain resin acids derived from the unmodified rosin or disproportionated rosin described above.

[0122] (Unmodified rosin ester) Unmodified rosin esters are obtained by reacting alcohols with the aforementioned unmodified rosin. Regarding the reaction conditions for the unmodified rosin and alcohols, the unmodified rosin and alcohols are reacted in the presence or absence of a solvent, with an esterification catalyst added as needed, at approximately 250°C to 280°C for approximately 1 to 8 hours. The alcohols mentioned are not particularly limited, and examples include: monohydric alcohols such as methanol, ethanol, propanol, and stearyl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and dimerized glycol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as neopentyl tetrol and diglycerol; and hexahydric alcohols such as dinepentyl tetrol. Among these, polyhydric alcohols having two or more hydroxyl groups are preferred, especially glycerol and neopentyl tetrol. The aforementioned alcohols can be used alone or in combination of two or more.

[0123] (Hydrogenated rosin ester) Hydrogenated rosin esters are obtained by further reacting the hydrogenated rosin obtained by hydrogenating the aforementioned unmodified rosin with alcohols and then esterifying it. Various known methods can be used to obtain the aforementioned hydrogenated rosin. Specifically, for example, the unmodified rosin can be heated under hydrogen pressure in the presence of a hydrogenation catalyst to cause a reaction (hydrogenation). Various known catalysts, such as supported catalysts and metal powders, can be used for the hydrogenation catalyst. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon; examples of metal powders include nickel and platinum. The amount of catalyst used is typically about 0.01 to 5 parts by mass relative to 100 parts by mass of the rosin used as raw material, preferably about 0.01 to 2 parts by mass. The hydrogen pressure during the hydrogenation of the unmodified rosin is about 2 MPa to 20 MPa, preferably about 5 MPa to 20 MPa. The reaction temperature for hydrogenating the unmodified rosin is approximately 100℃ to 300℃, with a preferred temperature of approximately 150℃ to 300℃.

[0124] Depending on the requirements, the above hydrogenation can also be carried out with the unmodified rosin dissolved in a solvent. The solvent used is not particularly limited; any solvent that is inert to the reaction system and readily dissolves the starting materials and products is acceptable. Specifically, for example, cyclohexane, n-hexane, n-heptane, decahydronaphthalene, tetrahydrofuran, and dihydronaphthalene can be used. One or more of the following, such as alkane, may be used, or a combination of two or more may be used. The amount of solvent used is not particularly limited; generally, it should be used in the range of 10% by mass or more, preferably 10% to 70% by mass, relative to the unmodified rosin. Regarding the reaction conditions of the hydrogenated rosin and alcohol, the hydrogenated rosin and alcohol are reacted with or without a solvent, with an esterification catalyst added as needed, at approximately 250°C to 280°C for approximately 1 to 8 hours. The alcohol used in the esterification of the hydrogenated rosin is the same as described above. Furthermore, the order of the hydrogenation reaction and the esterification reaction is not limited to the above; the hydrogenation reaction can also be carried out after the esterification reaction. In addition, the hydrogenated rosin ester obtained can be further subjected to the above hydrogenation reaction.

[0125] (Disproportionated rosin ester) Disproportionated rosin esters are obtained by further reacting the disproportionated rosin obtained by disproportionating the aforementioned unmodified rosin with alcohols and then esterifying it. Various known methods can be used to obtain the aforementioned disproportionated rosin. Specifically, for example, the unmodified rosin can be heated in the presence of a disproportionating catalyst to induce a reaction (disproportionation). Examples of disproportionating catalysts include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide. The amount of catalyst used is typically about 0.01 to 5 parts by mass relative to 100 parts by mass of the rosin used as raw material, preferably about 0.01 to 1 part by mass. The reaction temperature for disproportionating the aforementioned unmodified rosin is about 100°C to 300°C, preferably about 150°C to 290°C. Regarding the reaction conditions for disproportionated rosin and alcohols described above, the disproportionated rosin and alcohols are reacted in the presence or absence of a solvent, with the addition of an esterification catalyst as needed, and at approximately 250°C to 280°C for 1 to 8 hours. The alcohols used in the esterification of the disproportionated rosin are the same as those described above. Furthermore, the order of the disproportionation reaction and the esterification reaction is not limited to those described above; the disproportionation reaction can also be carried out after the esterification reaction.

[0126] (Polymeric rosin ester) Polymerized rosin esters are obtained by reacting polymerized rosin with alcohols. Polymerized rosin refers to rosin derivatives containing dimerized resin acids. Known methods can be used to manufacture the aforementioned polymerized rosin. Specifically, examples include: reacting the unmodified rosin as a raw material in a solvent such as toluene or xylene containing catalysts such as sulfuric acid, hydrogen fluoride, aluminum chloride, or titanium tetrachloride, at a reaction temperature of approximately 40°C to 160°C for approximately 1 to 5 hours. Specific examples of the aforementioned polymerized rosin include: gum-based polymerized rosin using gum rosin as a raw material (e.g., trade name "Polymerized Rosin B-140", manufactured by Shin-Zhou (Wuping) Forest Chemical Co., Ltd.); tall oil-based polymerized rosin using tall oil rosin as a raw material (e.g., trade name "SYLVATAC 140", manufactured by Arizona Chemical Co., Ltd.); and wood-based polymerized rosin using wood rosin as a raw material (e.g., trade name "Dimalex", manufactured by Hercules Co., Ltd.). Furthermore, for the aforementioned polymerized rosin, various treatments such as hydrogenation, disproportionation, acrylate modification, maleization, and fumaration of α,β-unsaturated carboxylic acids can also be used. These treatments can be performed individually or in combination of two or more. Regarding the reaction conditions of the aforementioned polymerized rosin with alcohols, the polymerized rosin and alcohols are reacted at approximately 250°C to 280°C for approximately 1 to 8 hours, with or without a solvent, and with an esterification catalyst added as needed. Alternatively, the aforementioned unmodified rosin can be further reacted with alcohols. The alcohols used during the esterification of the polymerized rosin are the same as described above. Furthermore, the order of the polymerization reaction and the esterification reaction is not limited to the above; the polymerization reaction can also be carried out after the esterification reaction.

[0127] (α,β-Unsaturated carboxylic acid modified rosin ester) α,β-Unsaturated carboxylic acid-modified rosin esters are obtained by reacting alcohols with the aforementioned α,β-unsaturated carboxylic acid-modified rosin. The reaction conditions for the α,β-unsaturated carboxylic acid-modified rosin and alcohols are not particularly limited; examples include adding alcohols to molten α,β-unsaturated carboxylic acid-modified rosin under heating and reacting at approximately 250°C to 280°C for approximately 15 to 20 hours. Furthermore, the above reaction can also be carried out while blowing inert gases such as nitrogen into a closed reaction system, or the aforementioned catalyst can be used. The alcohols used in the esterification of the α,β-unsaturated carboxylic acid-modified rosin are the same as described above.

[0128] (Rosin resin) Rosin phenol resin is obtained by reacting phenols with the aforementioned unmodified rosin. Regarding the phenols, there is no particular limitation; various known phenols can be used. Specifically, examples include alkylphenols such as cresol, butylphenol, octylphenol, and nonylphenol, phenol, bisphenols, and naphthols. These can be used individually or in mixtures of two or more. The amount of phenol used is typically about 0.8 to 1.5 mol relative to 1 mol of the aforementioned raw rosin. Regarding the manufacturing method of the aforementioned rosin phenol resin, there is no particular limitation; for example, a method in which the aforementioned unmodified rosin and phenols are reacted by heating in the presence of an acid catalyst as needed. Regarding the reaction temperature, a reaction at 180 to 350°C for approximately 6 to 18 hours is typically sufficient. Furthermore, the acid catalyst used in this reaction is not particularly limited, and examples include inorganic acid catalysts such as sulfuric acid, hydrogen chloride, and boron trifluoride, and organic acid catalysts such as p-toluenesulfonic acid and methanesulfonic acid. When using an acid catalyst, approximately 0.01 to 1.0 parts by weight are sufficient relative to 100 parts by weight of the aforementioned unmodified rosin. Additionally, the rosin phenol resin can also be esterified by further reacting an alcohol with the resin obtained in the above reaction. The alcohol used in this case is the same as described above.

[0129] (Rosin polyols) Rosin polyols are compounds having at least two rosin skeletons and at least two hydroxyl groups within their molecules. Examples of rosin polyols include the reaction products of unmodified rosin, hydrogenated rosin, or disproportionated rosin with epoxy resins (see Japanese Patent Application Publication No. 5-155972). Examples of epoxy resins include bisphenol type epoxy resins, phenolic varnish type epoxy resins, resorcinol type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, aliphatic polyepoxides, alicyclic epoxy compounds, glycidylamine type epoxy compounds, glycidyl ester type epoxy compounds, monoepoxides, naphthyl epoxy compounds, biphenyl type epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy-containing polyester resins, epoxy-containing polyurethane resins, epoxy-containing acrylic resins, stilbene type epoxy compounds, and tri-epoxides. Type epoxides, cyclopentadiene epoxides, triphenol methyl epoxides, alkyl-modified triphenol methyl epoxides, dicyclopentadiene epoxides, aryl alkylene epoxides, etc.

[0130] Examples of bisphenol-type epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol AD ​​type epoxy resin, tetrabromobisphenol A type epoxy resin, etc.

[0131] Examples of the aforementioned phenolic varnish-type epoxy resins include: cresol phenolic varnish-type epoxy resin, phenolic varnish-type epoxy resin, α-naphthol phenolic varnish-type epoxy resin, bisphenol A type phenolic varnish-type epoxy resin, brominated phenolic varnish-type epoxy resin, etc.

[0132] Examples of the aforementioned aliphatic polyepoxide compounds include: 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, and diglycidyl ether.

[0133] Examples of the aforementioned alicyclic epoxide compounds include: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-di Alkane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6'-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethyl bis(3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, etc.

[0134] Examples of the aforementioned glycidylamine type epoxy compounds include: tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-m-phenylenediamine, etc.

[0135] Examples of the glycidyl ester type epoxy compounds mentioned above include: diglycidyl phthalate, hexahydrodiglycidyl phthalate, tetrahydrodiglycidyl phthalate, etc.

[0136] The method for manufacturing the aforementioned rosin polyol is not particularly limited. For example, the following method can be used: a ring-opening addition reaction is carried out between the aforementioned unmodified rosin, hydrogenated rosin, or disproportionated rosin and epoxy resin at 120°C to 200°C in the presence of a catalyst. Regarding the catalyst, examples that can be used include: amine catalysts such as trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, and 2-methylimidazole; fourth-order ammonium salts such as benzyltrimethylammonium chloride; Lewis acid; borate esters; organometallic compounds; and organometallic salts.

[0137] The softening point of the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher is 80℃~200℃. Considering the excellent mechanical strength, controllability and processability of fiber-reinforced resins, the preferred temperature is around 80℃~180℃, and the more preferred temperature is around 90℃~160℃.

[0138] The number average molecular weight of rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher is preferably 100 to 50,000. A number average molecular weight of 100 or higher improves the flexural and tensile strength of the molded article. More preferably, the number average molecular weight is 300 or higher, further preferably 500 or higher, and most preferably 1,000 or higher. Furthermore, a number average molecular weight of 50,000 or lower results in a moderately low viscosity for rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher, thus providing excellent impregnation of reinforcing fibers (A) contained in the molded article and improving the dispersibility of reinforcing fibers (A) in the molded article. More preferably, the number average molecular weight is 25,000 or lower, further preferably 15,000 or lower, and even more preferably 10,000 or lower. Moreover, the number average molecular weight of such a compound can be determined using gel permeation chromatography (GPC).

[0139] Relative to a total of 100 parts by weight of carbon fiber (A), thermoplastic resin (B), and rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, the content of rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher in the composition of the present invention is 0.5 to 30 parts by weight. If the content of rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher is 0.5 parts by weight or higher, the flowability and dispersibility of the reinforcing fiber (A) in the molded article are further improved. Preferably, it is 1 part by weight or higher, more preferably 2 parts by weight or higher. On the other hand, if the content of rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher is 30 parts by weight or less, the tensile strength and impact strength of the molded article are further improved. Preferably, it is 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less.

[0140] Rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, preferably exhibits a heat loss of 5% by weight or less when heated at a rate of 10°C / min (in air) during molding. More preferably, it is 3% by weight or less, and even more preferably, it is 1.5% by weight or less. When such a heat loss is 5% by weight or less, the generation of decomposition gases during impregnation into the reinforcing fiber (A) can be suppressed, and the generation of voids during molding can be suppressed. Furthermore, gas generation can be suppressed, especially during molding at high temperatures.

[0141] Here, the weight loss of rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher at the molding temperature can be obtained by thermogravimetric analysis (TGA) using a platinum sample pan in an air environment at a heating rate of 10°C / min.

[0142] Without prejudice to the purpose of this invention, the molded articles and molding materials of this invention may contain other components besides those described in (A) to (C). Examples of such other components include: thermosetting resins, inorganic fillers other than carbon fibers, flame retardants, nucleating agents, ultraviolet absorbers, antioxidants, shock absorbers, vibration dampers, antibacterial agents, insect repellents, deodorizing agents, anti-coloring agents, heat stabilizers, release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, foaming agents, or coupling agents, etc.

[0143] Secondly, regarding the molding method for molded articles using molding materials composed of the components of the present invention, a molding method using a mold is preferred, and various molding methods such as injection molding, extrusion molding, and compression molding can be used. In particular, by using an injection molding machine, stable molded articles can be obtained continuously. Regarding the injection molding conditions, there are no particular provisions, but the following conditions are preferred: injection time: 0.1 seconds to 20 seconds, more preferably 1 second to 10 seconds; back pressure: 0.1 MPa to 20 MPa, more preferably 3 MPa to 15 MPa; holding pressure: 1 MPa to 150 MPa, more preferably 5 MPa to 100 MPa; holding time: 1 second to 30 seconds, more preferably 5 seconds to 20 seconds; barrel temperature: 180°C to 350°C; and mold temperature: 20°C to 160°C. Here, the barrel temperature refers to the temperature of the part of the injection molding machine that heats and melts the molding material, and the mold temperature refers to the temperature of the mold used to inject resin to form a specified shape. By appropriately selecting these conditions, especially the injection time, back pressure and mold temperature, the fiber length of the reinforcing fiber in the molded article can be easily adjusted to satisfy the formula described later [1].

[0144] In the composition of the present invention (in the molding material composed of the composition of the present invention), the weight-average fiber length (Lw) of the reinforcing fiber (A) is 0.1 to 7.0 mm. If the weight-average fiber length (Lw) is 0.1 mm or more, the mechanical properties of the molded article, especially the bending strength and tensile strength, will be further improved. Lw is preferably 0.3 mm or more. On the other hand, if the weight-average fiber length (Lw) is 7 mm or less, the dispersion of the reinforcing fiber (A) between individual yarns will be further improved, and thus the mechanical properties and appearance quality of the molded article will be further improved. Lw is more preferably 5 mm or less, and more preferably 4 mm or less. Here, the term "weight-average fiber length" in the present invention refers to the weight-average fiber length calculated by applying the method of calculating the weight-average molecular weight to calculate the fiber length, and is not simply an average, but a weight-average fiber length calculated from the following formula considering the contribution of the fiber length. However, the following formula is applied when the fiber diameter and density of the reinforcing fiber (A) are fixed. Average fiber length by weight = Σ(Mi²×Ni) / Σ(Mi×Ni) Mi: Fiber length (mm) Ni: The number of reinforcing fibers in fiber length Mi.

[0145] The weight-average fiber length can be determined using the following method. Using an optical microscope equipped with a heated stage, a test piece is appropriately cut from the molded article. The thermoplastic resin (B) is heated between glass plates on a heated stage set at a temperature of 150–350°C to form a thin film that is uniformly dispersed. The film is then observed using 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) 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 a suitable heating treatment is applied to create 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 using an optical microscope (50–200x magnification). The fiber length of 1000 randomly selected reinforcing fibers (A) is measured, and the weight-average fiber length (Lw) 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.

[0146] Next, the morphology when using the composition of the present invention as a molding material will be described. The molding material of this invention preferably comprises a fiber bundle containing reinforcing fibers (A) forming a continuous fiber bundle within a thermoplastic resin (B). Alternatively, it may comprise a composite in which rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher is filled between the individual fibers of the fiber bundle. The composite is formed by impregnating the fiber bundle with rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, wherein the reinforcing fibers (A) are dispersed in an island-like manner within a sea of ​​rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher. The molding material of this invention preferably contains thermoplastic resin (B) on the outer surface of the aforementioned fiber bundle or composite. The desired configuration is as follows: in a cross section perpendicular to the long side direction of the molding material, thermoplastic resin (B) is arranged around the fiber bundles or composite; or the fiber bundles or composite are arranged in layers with thermoplastic resin (B), and the outermost layer is thermoplastic resin (B).

[0147] When the molding material of the present invention contains rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher, the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher is often of low molecular weight and is usually a relatively brittle and easily broken solid or liquid at room temperature. By forming a structure in which a thermoplastic resin (B) is included on the outside of the composite, the high molecular weight thermoplastic resin (B) protects the composite and inhibits the breakage and scattering of the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher caused by impact, abrasion, etc. during handling or operation of the molding material, thus maintaining the shape of the molding material. From an operability point of view, the molding material of the present invention preferably maintains the aforementioned shape until it is fed into the molding process.

[0148] When the composition of the present invention is used as a molding material, any rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher may be included in the raw materials. It may be included in fiber bundles or composites, in thermoplastic resin (B), or in both. Examples include: a composition comprising thermoplastic resin (B) and rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher, covered with fiber bundles or composites; a rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or higher impregnated into fiber bundles (F); or a rosin resin (C) attached to the surface of reinforcing fiber (A) or included within a single yarn, etc.

[0149] The composite and the thermoplastic resin (B) and the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher can be in a state where the thermoplastic resin (B) and the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher partially enter into a part of the composite and are in a state of being miscible, or the thermoplastic resin (B) and the rosin resin (C) with an acid value and / or hydroxyl value of 100 mg KOH / g or higher can be infiltrated into the fiber bundle.

[0150] When the composition of the present invention is used as a molding material, in cases where the molding material contains two types of reinforcing fibers, it is preferable that the two reinforcing fibers, such as carbon fibers and organic fibers or glass fibers, are unevenly distributed in the fiber bundle cross-section. Here, the term "fiber bundle cross-section" refers to a cross-section perpendicular to the long side direction of the fiber bundle. By unevenly distributing carbon fibers and organic fibers or glass fibers in the fiber bundle cross-section, entanglement of carbon fibers and organic fibers or glass fibers during molding is suppressed, resulting in a molded article with uniformly dispersed carbon fibers and organic fibers or glass fibers. Therefore, the mechanical properties of the molded article, especially its impact strength and appearance quality, can be further improved. Here, the term "uneven distribution" in the present invention refers to the fact that, in the fiber bundle cross-section, carbon fibers and organic fibers or glass fibers are not equally present throughout the entire area, but rather partially present. Examples of "non-uniform distribution" in this invention include, for instance, core-sheath structures where carbon fibers enclose organic or glass fibers in the fiber bundle cross-section, or where organic or glass fibers enclose carbon fibers; or structures where the bundles of carbon fibers and the bundles of organic or glass fibers exist separately in the fiber bundle cross-section, separated by a boundary portion. Furthermore, the term "enclosed" in this invention refers to a configuration where carbon fibers are disposed in the core and organic or glass fibers are disposed in the sheath, or a configuration where organic or glass fibers are disposed in the core and carbon fibers are disposed in the sheath. In the fiber bundle cross-section, at least a portion of both the carbon fibers and the organic or glass fibers are in contact with the outer thermoplastic resin (B). In this case, the configuration where the carbon fibers, organic fibers, or glass fibers are in contact with the thermoplastic resin (B) also includes configurations where the carbon fibers, organic fibers, or glass fibers are in contact with the thermoplastic resin (B) through the aforementioned rosin resin (C).

[0151] Furthermore, in this invention, for the method of confirming the uneven distribution of carbon fibers, organic fibers or glass fibers in the fiber bundle, examples can be given, such as: observing a cross section perpendicular to the long side direction of the fiber of the forming material using an optical microscope with a magnification set to 300x, and then processing and analyzing the obtained microscope image.

[0152] Next, a method for manufacturing the molding material of the present invention will be described. The molding material of the present invention can be obtained by known manufacturing methods, and is not limited to the following methods. For example, it can be obtained by the following methods.

[0153] First, the rovings of reinforcing fiber (A) are yarn doubling side-by-side along the long side of the fiber to create a fiber bundle containing reinforcing fiber (A). Second, if necessary, the aforementioned molten rosin resin (C) is impregnated into the fiber bundle to create a composite. Further, the fiber bundle or composite is guided into an impregnation mold filled with molten thermoplastic resin (B), such that the resin composition containing thermoplastic resin (B) is coated on the outside of the fiber bundle or composite, and then extracted through a nozzle. For example, a method of obtaining a molded material by granulating it to a predetermined length after cooling and solidification can be used. As long as the thermoplastic resin (B) is contained on the outside of the composite, it can also be impregnated into the fiber bundle.

[0154] Furthermore, the molten rosin resin (C) can be impregnated into the fiber bundle produced by the aforementioned method to create a composite, and the thermoplastic resin (B) can be coated on the outside of the composite. When the thermoplastic resin (B) is bonded to the surface of the fiber bundle composed of reinforcing fibers (A), the preferred bonding method is to prepare the molten thermoplastic resin (B) to contact the surface of the fiber bundle and then cool / cur it. The method is not particularly limited, but more specifically, examples include: using an extruder and a coating die for wire coating to prepare the thermoplastic resin (B) to continuously coat the fiber bundle; or using an extruder and a T-die to prepare a thin film of molten thermoplastic resin (B) from one or both sides of a fiber bundle flattened by rollers, and then integrating it using rollers, etc.

[0155] For example, Figures 2 and 3 are schematic diagrams showing an example of a preferred cross-sectional shape of the molding material of the present invention. Symbol 1 represents reinforcing fiber (A), symbol 2 represents thermoplastic resin (B), symbol 3 represents rosin resin (C), and symbol 4 represents fiber bundle.

[0156] The cross-sectional shape of the molding material is not limited to that shown in the figure, as long as the thermoplastic resin (B) is attached to the outside of the fiber bundle.

[0157] The cross-section of the molding material is shown in the longitudinal section of Figure 2. Preferably, it is configured such that fiber bundles form the core material and are sandwiched in layers of thermoplastic resin (B). Furthermore, as shown in the cross-section of Figure 3, it is also preferable to configure a core-sheath structure with fiber bundles as the core structure and thermoplastic resin (B) covering the surrounding area. In addition, as shown in Figure 4, it is also preferable to configure a structure in which thermoplastic resin (B) covers multiple fiber bundles. In this case, it is desirable that the number of fiber bundles is about 2 to 6. Furthermore, Figure 1 is a schematic diagram showing an example of the cross-sectional shape of the fiber bundle in the present invention. As shown in Figure 1, the fiber bundle of the present invention is filled with rosin resin (C) between each individual fiber 1 of the reinforcing fiber (A). That is, the individual fibers of the reinforcing fiber (A) are dispersed like islands in a sea of ​​rosin resin (C). Furthermore, in this invention, a longitudinal section refers to a cross-section on a plane including the axial direction, and a transverse section refers to a cross-section on a plane perpendicular to the axial direction. Additionally, when the forming material is, for example, a cylindrical granular material, the axial direction refers to the axis of the cylinder.

[0158] Furthermore, the length of the reinforcing fiber (A) is substantially the same as the length of the molding material. This can be clearly seen from, for example, the pattern in Figure 3. The molding material shown in Figure 3 consists of individual fibers of the reinforcing fiber (A) arranged approximately side-by-side along the axial direction (same direction) of the molding material, and the length of the reinforcing fiber (A) is substantially the same as the length of the molding material. In Figure 3, the black dots represent the reinforcing fiber (A), and the white parts represent rosin resin (C). Since the length of the fiber bundle is substantially the same as the length of the molding material, the fiber length of the reinforcing fiber (A) in the molded product can be increased, thus achieving superior mechanical properties.

[0159] The phrase "arranged roughly side by side" here means that the axis of the long axis of the reinforcing fiber (A) and the axis of the long axis of the molding material point in the same direction. The angle between the axes is preferably 20° or less, more preferably 10° or less, and even more preferably 5° or less. Furthermore, "substantially the same length" means that the reinforcing fiber (A) is not intentionally cut within the molding material, or that it substantially does not contain reinforcing fibers (A) significantly shorter than the total length of the molding material. This is not to specifically limit the amount of reinforcing fibers (A) shorter than the total length of the molding material, but the content of reinforcing fibers (A) accounting for less than 50% of the total length of the molding material is preferably less than 30% by mass, more preferably less than 20% by mass of all reinforcing fibers (A). By having the reinforcing fiber (A) of substantially the same length as the molding material, the length of the reinforcing fiber (A) in the molded article can be increased, and tensile strength and impact strength can be improved. The length of the reinforcing fiber (A) and the molding material is preferably less than 18 mm and more than 3 mm, and more preferably less than 15 mm and more than 5 mm. The molding material preferably maintains a substantially uniform cross-sectional shape and is continuous in the long side direction.

[0160] Next, an example of a method for manufacturing the forming material in this invention will be described. In this invention, the method for obtaining fiber bundles by impregnating rosin resin (C) into reinforcing fibers (A) is not particularly limited. Examples include methods having the following steps (I) and (II). Step (I) involves supplying rosin resin (C) to the reinforcing fibers (A) and contacting the rosin resin (C) (or other resins may be blended into the rosin resin. In this case, other resins are attached to and impregnated into the reinforcing fibers (A) in the same way as the rosin resin (C)) in a molten state at 100-300°C, thereby attaching the rosin resin (C) to the reinforcing fibers (A). Step (II) involves heating the reinforcing fibers (A) with the attached rosin resin (C) to impregnate them.

[0161] In step (I) above, the method of supplying rosin resin (C) and attaching it to the reinforcing fiber (A) is not particularly limited, and any method used when applying oil, sizing agent, or matrix resin to the reinforcing fiber (A) can be used. Among these, dipping or coating is preferred.

[0162] Here, "impregnation" refers to a method of supplying rosin resin (C) to a molten bath using a pump and passing the reinforcing fiber (A) through the molten bath. By immersing the reinforcing fiber (A) in the molten bath of rosin resin (C), the rosin resin (C) can be reliably adhered to the reinforcing fiber (A). Furthermore, "coating" refers to a method of applying rosin resin (C) to the reinforcing fiber (A) using coating methods such as reverse roller type, forward roller type, contact coating roller type, spray type, and curtain type. Here, "reverse roller type," "forward roller type," and "contact coating roller type" refer to methods of supplying molten rosin resin (C) to a roller using a pump and applying the molten rosin resin (C) to the reinforcing fiber (A). Further, the reverse roller type is a method in which two rollers rotate in opposite directions and the molten rosin resin (C) is applied to the rollers; the forward roller type is a method in which two rollers rotate in the same direction and the molten rosin resin (C) is applied to the rollers. Generally, in reverse-roller and forward-rotating roller methods, the reinforcing fiber (A) can be clamped, and the roller can be further positioned to ensure the rosin resin (C) adheres securely. On the other hand, the contact roller method adheres the rosin resin (C) simply by having the reinforcing fiber (A) come into contact with the roller. Therefore, the contact roller method is preferable for applications with relatively low viscosity. However, regardless of the roller method used, a specified amount of heated molten rosin resin (C) can be applied, allowing the rosin resin to adhere to each unit length of fiber while it is traveling in contact with the reinforcing fiber (A). The spray method utilizes the principle of spraying, causing the molten rosin resin (C) to be atomized and sprayed onto the reinforcing fiber (A). The curtain method involves coating the molten rosin resin (C) by allowing it to fall naturally from small holes or by allowing it to overflow from a melting tank. Because the amount of rosin resin (C) to be applied is easily adjustable, the loss of rosin resin (C) can be reduced.

[0163] Furthermore, the melting temperature (temperature in the melt bath) when supplying rosin resin (C) is preferably 100~300°C. A melting temperature above 100°C moderately suppresses the viscosity of the rosin resin (C), thus preventing uneven adhesion. More preferably, it is 150°C or higher. On the other hand, a melting temperature below 300°C suppresses the thermal decomposition of the rosin resin (C) even under prolonged manufacturing conditions. More preferably, it is 250°C or lower. By contacting the reinforcing fiber (A) in a molten state at 100~300°C, rosin resin (C) can be stably supplied.

[0164] Next, step (II) will be explained regarding the step of heating the reinforcing fiber (A) with rosin resin (C) obtained in step (I) to impregnate it. Specifically, this step involves applying tension using rollers or bars to the reinforcing fiber (A) with rosin resin (C) at a temperature where the rosin resin (C) melts; repeatedly widening and bundling it; applying pressure or vibration, etc., to impregnate the reinforcing fiber (A) with rosin resin (C). As a more specific example, methods such as widening the reinforcing fiber (A) by passing it through the surfaces of multiple heated rollers or bars can be listed, among which the impregnation method using extrusion nozzles, extrusion rollers, roller presses, and double-belt presses is particularly suitable. Here, an extrusion nozzle is a nozzle whose nozzle diameter narrows in the direction of penetration, which simultaneously bundles the reinforcing fiber (A), scrapes off excess rosin resin (C), and promotes impregnation. Furthermore, a so-called extrusion roller applies tension to the reinforcing fiber (A) to scrape off excess rosin resin (C) while simultaneously promoting impregnation. Additionally, a roller press uses the pressure between two rollers to continuously remove air from the reinforcing fiber (A) while simultaneously promoting impregnation; a so-called double-belt press uses a belt to press the reinforcing fiber (A) from above and below, thereby promoting impregnation.

[0165] Furthermore, in step (II), it is preferable that 80-100% by weight of the supplied amount of rosin resin (C) is impregnated into the reinforcing fiber (A). Since this directly affects the yield, from an economic and productivity point of view, the higher the impregnation amount relative to the supplied amount, the better. More preferably, it is 85-100% by weight, and even more preferably, it is 90-100% by weight. In addition, if it is 80% by weight or more, in addition to the economic point of view, it will also suppress the generation of volatile components caused by rosin resin (C) in step (II), and can suppress the formation of voids inside the fiber bundle.

[0166] Furthermore, in step (II), the maximum temperature of the rosin resin (C) is preferably 150 to 400°C. If the maximum temperature is 150°C or higher, it is more preferably 180°C or higher, and even more preferably 200°C or higher. On the other hand, if the maximum temperature is below 400°C, undesirable side reactions such as the decomposition reaction of the rosin resin (C) can be suppressed. It is more preferably 380°C or lower, and even more preferably 350°C or lower.

[0167] The heating method in step (II) is not particularly limited, but specific examples include: using a heated chamber, using a hot roller to simultaneously heat and pressurize, etc.

[0168] Furthermore, from the viewpoint of suppressing undesirable side reactions such as cross-linking and decomposition of rosin resin (C), it is preferable to perform heating in a non-oxidizing gas environment. Here, a non-oxidizing gas environment refers to a gas environment with an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, and even more preferably an oxygen-free gas environment, i.e., an inert gas environment such as nitrogen, helium, or argon. In particular, from the perspective of economy and ease of operation, a nitrogen gas environment is preferred.

[0169] Furthermore, in the preceding stages of steps (I) and (II) mentioned above, the reinforcing fiber (A) bundle can also be pre-opened. Opening refers to the operation of separating the bundled reinforcing fiber bundle, which is expected to further improve the permeability of rosin resin (C). By opening the reinforcing fiber bundle, the thickness becomes thinner. When the width of the reinforcing fiber bundle before opening is defined as b1 (mm) and the thickness as a1 (μm), and the width of the reinforcing fiber bundle after opening is defined as b2 (mm) and the thickness as a2 (μm), it is preferable to set the opening ratio = (b2 / a2) / (b1 / a1) to 2.0 or more, and even more preferably to 2.5 or more.

[0170] There are no particular limitations on the method of opening the reinforcing fiber bundle. For example, the following methods can be used: alternating passing of concave and convex rollers, using a drum-shaped roller, applying tension variation to axial vibration, causing tension variation of the reinforcing fiber bundle by two friction bodies reciprocating vertically, and blowing air onto the reinforcing fiber bundle.

[0171] A molded material can be obtained by coating such fiber bundles with a thermoplastic resin (B) or a resin composition containing at least a thermoplastic resin (B).

[0172] Furthermore, a molding material mixture can be obtained by dry blending the following two: a molding material formed by coating a fiber bundle produced by the aforementioned method with thermoplastic resin (B), and granules formed by melt-blending thermoplastic resin (B). In this case, the content of reinforcing fiber (A) in the molded article can be easily adjusted. Alternatively, a molding material mixture can be obtained by pellet blending the following two: a molding material formed by coating a composite containing carbon fiber and the aforementioned rosin resin (C) with thermoplastic resin (B), and a molding material formed by coating a composite containing organic fiber or glass fiber and the aforementioned rosin resin (C) with thermoplastic resin (B). Here, dry blending, unlike melt blending, refers to stirring / mixing multiple materials at a temperature where the resin components do not melt, resulting in a substantially homogeneous state. This method is particularly suitable for injection molding, extrusion molding, and other applications using granular molding materials.

[0173] The molding material mixture preferably comprises: a carbon fiber reinforced thermoplastic resin molding material (X) (sometimes referred to as "carbon fiber reinforced molding material") comprising at least carbon fibers, thermoplastic resin (B), and the aforementioned rosin resin (C); and an organic fiber / or glass fiber reinforced thermoplastic resin molding material (Y) (sometimes referred to as "organic fiber / or glass fiber reinforced molding material") comprising at least organic fibers or glass fibers, thermoplastic resin (B), and the aforementioned rosin resin (C). The carbon fiber reinforced molding material (X) comprises a composite formed by impregnating the aforementioned rosin resin (C) into the carbon fibers, preferably having a structure in which thermoplastic resin (B) is contained on the outer side of the composite, and preferably the length of the carbon fibers is substantially the same as the length of the carbon fiber reinforced thermoplastic resin molding material. Furthermore, the organic fiber / or glass fiber reinforced molding material (Y) comprises a composite formed by impregnating the aforementioned rosin resin (C) into the organic fiber / or glass fiber, and preferably has a structure in which thermoplastic resin (B) is contained on the outer side of the composite. Furthermore, the aforementioned rosin resin (C) can be the same type, and the thermoplastic resin (B) can also be the same type.

[0174] The composition of this invention is a fiber-reinforced thermoplastic resin composition with excellent tensile strength, impact strength, and appearance quality. Molded articles and materials made from the composition of this invention are extremely useful in applications such as electrical / electronic machinery, home appliances, housings, automotive parts, and sports components. Regarding electrical / electronic machinery housings and components, suitable applications include electronic components such as housings for computers, televisions, VCRs, DVD players, cameras, and audio equipment, as well as connectors, speakers, microphones, headphones, small electric motors, and computer-related components. Regarding home appliances, examples include: VTR components, television components, irons, hair dryers, rice cooker components, microwave oven components, audio equipment, laser discs (registered trademark), CDs, DVDs, and other audio-visual equipment components, lighting components, refrigerator components, air conditioner components, typewriter components, and word processor components. In addition, regarding optical instruments and precision machinery components, examples include: office computer components, telephone components, fax machine components, photocopier components, binoculars, cameras, clocks, etc. Regarding automotive components and vehicle-related parts, examples include: door pads, pillars, console boxes, various electric motor housings, roof rails, mudguards, garnishes, bumpers, door panels, roof panels, hood panels, trunk lids, door mirror stays, spoilers, hood louvers, wheel covers, wheel covers, grille apron cover frames, lamp bezels, door handles, door moldings, rear side panels, windshield wipers, etc. Furthermore, the components of this invention are also suitable as sporting goods, and can be appropriately used in: golf clubs and shafts, grips, golf balls and other golf-related products; tennis rackets and tennis balls, badminton rackets and their strings and shuttlecocks and other racket-related products; sports body protection products such as masks, helmets, chest protectors, elbow pads, and knee pads for American football, baseball, softball, etc.; shoe-related products such as sole materials for sports shoes; fishing tackle-related products such as fishing rods, reels, and lures; 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]

[0175] The present invention will be further described in detail in the following embodiments, but the present invention is not limited to the description of these embodiments. First, the evaluation methods for various characteristics used in this embodiment will be described.

[0176] (1) Weight average fiber length Test pieces cut from the molded articles were placed in a solvent in which the thermoplastic resin (B) used in the various examples and comparative examples would dissolve, and appropriate heat treatment was applied to obtain a solution in which the reinforcing fibers (A) were uniformly dispersed. Subsequently, the solution was 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 1000 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: The number of fibers in the fiber length Mi.

[0177] (2) Tensile strength test of molded articles For the ISO-type dumbbell-shaped test pieces obtained from the various embodiments and comparative examples, tensile tests were conducted using an Autograph AG-20kNX tensile testing machine (manufactured by Shimadzu Corporation) at a tensile speed of 5 mm / min, in accordance with ISO 527 (2012), and the maximum point stress was determined.

[0178] (3) Charpy impact strength test of molded articles The parallel portions of the ISO-type dumbbell-shaped test pieces obtained from the various examples and comparative examples were cut out. The Charpy V-notch impact test was performed according to ISO 179 using a Tokyo Testing Machine Co., Ltd. C1-4-01 testing machine, and the impact strength (kJ / cm2) was calculated.

[0179] (4) Determination of acid value / hydroxyl value of rosin resin (C) The acid value / hydroxyl value of the test sample was determined according to JIS K 0070.

[0180] (5) Determination of heat loss of rosin resin (C) Thermogravimetric analysis (TGA) was used to determine the weight loss of the test samples. A platinum sample pan was used, and the temperature was increased at 10 °C / min under a nitrogen atmosphere. The weight loss rate at 270 °C was measured.

[0181] (6) Appearance evaluation of the molded product (blackness evaluation) For test pieces with a thickness of 80mm × 80mm × 3mm obtained from the various embodiments and comparative examples, the L* value in the appearance of the molded product surface was measured using a spectrophotometer (SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.). The measurement was performed three times, and the average value was used for the evaluation of each embodiment and comparative example. A and B were determined to be acceptable based on the following criteria. A:L* is below 18 B:L* is below 20 C:L* series 20 and above

[0182] (7) Appearance evaluation of molded products (fiber dispersion evaluation) The number of undispersed fiber bundles present on each surface of the test piece used for the drop hammer impact strength test, obtained from each embodiment and comparative example, was visually counted. The evaluation was conducted on 50 molded pieces, and the fiber dispersion was determined based on the total number of bundles using the following criteria, with A and B being deemed acceptable. A: Less than 1 undispersed CF beam B: More than one undispersed CF bundle C: More than two undispersed CF bundles

[0183] Reference Example 1 Production of carbon fiber (A-1) Continuous carbon fibers with a total yarn count of 24,000, 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, sintering, and surface oxidation of a copolymer with polyacrylonitrile as the main component. 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 mother liquor was prepared by dissolving glycerol polyglycidyl ether, a multifunctional compound, in water to 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%.

[0184] Manufacturing Example 1 Production of rosin resin (C-2) 100 parts of hydrogenated rosin were fed into a reaction apparatus equipped with a stirring device, a cooling pipe and a nitrogen inlet pipe. After being heated under a nitrogen flow to completely melt the rosin, 190 parts of bisphenol A type high molecular weight epoxy resin (epoxy equivalent 500) were added while stirring. 0.1 parts of 2-methylimidazole were added at 140°C and the reaction was carried out at 180°C for 3 hours to obtain rosin resin (C-2) with a hydroxyl value of 150 mgKOH / g.

[0185] Manufacturing Example 2 Production of rosin resin (C-3) 100 parts of hydrogenated rosin were fed into a reaction apparatus equipped with a stirring device, a cooling pipe and a nitrogen inlet pipe. After being heated under a nitrogen flow to completely melt the rosin, 230 parts of bisphenol A type high molecular weight epoxy resin (epoxy equivalent 500) were added while stirring. 0.1 parts of 2-methylimidazole were added at 140°C and the reaction was carried out at 180°C for 3 hours to obtain rosin resin (C-3) with a hydroxyl value of 200 mgKOH / g.

[0186] Manufacturing Example 3 Production of rosin resin (C-5) 200 parts of disproportionated rosin were fed into a reaction apparatus equipped with a stirrer, a cooling pipe, and a nitrogen inlet pipe. After complete melting under a nitrogen stream, 109 parts of bisphenol A type epoxy resin (epoxy equivalent 180) were added while stirring. 0.06 parts of 2-methylimidazole were added at 140°C, and the reaction was carried out at 150°C for 5 hours, thereby obtaining a rosin polyol with a hydroxyl value of 125 mgKOH / g. Subsequently, 112 parts of domestically produced rubber rosin were added, and the reaction was carried out at 275°C for 2 hours, yielding a rosin resin (C-5) with a hydroxyl value of 43 mgKOH / g.

[0187] Manufacturing Example 4 Production of rosin resin (C-6) 200 parts of disproportionated rosin were fed into a reaction apparatus equipped with a stirrer, a cooling pipe, and a nitrogen inlet pipe. After complete melting under a nitrogen stream, 109 parts of bisphenol A type epoxy resin (epoxy equivalent 180) were added while stirring. 0.06 parts of 2-methylimidazole were added at 140°C, and the reaction was carried out at 150°C for 5 hours to obtain a rosin polyol with a hydroxyl value of 125 mgKOH / g. Subsequently, 56 parts of domestically produced rubber rosin were added, and the reaction was carried out at 275°C for 2 hours to obtain a rosin resin (C-6) with a hydroxyl value of 75 mgKOH / g.

[0188] Organic fibers (A-2) It uses liquid crystal polyester fiber (Toray "Siveras" (registered trademark) 1700T-288f, strength: 23.5cN / dtex, melting point 330℃, energy propagation speed: 17.3km / s).

[0189] Fiberglass (A-3) Glass fiber roving (manufactured by Asahi Fiber, “ER2220”, fiber diameter: 16μm, using aminosilane coupling agent, olefin emulsion, filament count: approximately 4000) was used.

[0190] Thermoplastic resin (B) (B-1) Polyamide resin (Toray Corporation, Nylon 6 resin "Amilan" (registered trademark) CM1001) was used.

[0191] (B-2) Polyamide resin (Toray Corporation, Nylon 610 resin "Amilan" (registered trademark) CM2001) was used.

[0192] (B-3) Polyamide resin (Arkema, Inc., Rilsan 11 resin "Rilsan" (registered trademark) BMN O) was used.

[0193] (B-4) Polyamide resin (Arkema, Inc., Rilsamid 12 resin "Rilsamid" (registered trademark) AMN O) was used.

[0194] (B-5) Polyamide resin (Kuraray, Inc., Nylon 9T resin "Genestar" (registered trademark) N1000A) was used.

[0195] (B-6) It was prepared by granulating polypropylene resin (Prime Polypro, a registered trademark) J137 manufactured by Prime Polymer Co., Ltd. and maleic acid modified polypropylene resin (Admer, a registered trademark) QE840 manufactured by Mitsui Chemicals Co., Ltd.) at a weight ratio of 85 / 15.

[0196] (B-7) It uses polycarbonate resin (Teijin Chemicals Co., Ltd., "Panlite" (registered trademark) L-1225L).

[0197] (B-8) Polyarylene sulfide resin (Toray, Ltd., PPS resin "Torelina" (registered trademark) M2888) was used.

[0198] Thermoplastic resin (Ba) (Ba-1) Polyamide resin (Toray Corporation, Nylon 6 resin "Amilan" (registered trademark) CM1001) was used.

[0199] (Ba-2) Polyamide resin (Arkema, Inc., Rilsamid 12 resin "Rilsamid" (registered trademark) AMN O) was used.

[0200] Resins with reactive functional groups (Bb) (Bb-1): Glycidyl methacrylate modified polyethylene copolymer "Bondfast" (registered trademark) BF-7L (manufactured by Sumitomo Chemical Co., Ltd.).

[0201] (Bb-2): Glycidyl methacrylate modified polyethylene copolymer "Bondfast" (registered trademark) BF-7M (manufactured by Sumitomo Chemical Co., Ltd.).

[0202] (Bb-3): Maleic anhydride modified ethylene-1-butene copolymer "Tafmer" (registered trademark) MH7020 (Mitsui Chemicals, Inc.)

[0203] Rosin resin (C) (C-1) Highly polar rosin was used: (Pine Crystal D-6011 manufactured by Arakawa Chemical Industry Co., Ltd. (registered trademark), hydroxyl value 100mgKOH / g, loss of heat at 270℃: 1.8%).

[0204] (C-2) Rosin resin (C-2) obtained from Manufacturing Example 1 (with a heat loss at 270°C: 1.4%) was used.

[0205] (C-3) Rosin resin (C-3) obtained from Manufacturing Example 2 (with a heat loss of 0.8% at 270°C) was used.

[0206] (C-4) Acid-modified rosin was used: (Pine Crystal KE604 manufactured by Arakawa Chemical Industry Co., Ltd. (registered trademark), acid value 230 mg KOH / g, loss of heat at 270°C: 9.6%).

[0207] (C-5) Rosin resin (C-5) obtained from Manufacturing Example 3 (with a heat loss of 1.6% at 270°C) was used.

[0208] (C-6) Rosin resin (C-6) obtained from Manufacturing Example 4 (with a heat loss of 2.2% at 270°C) was used.

[0209] Resin (D) used in the comparative example (D-1) Terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., "YS Polystar N125 (trade name)", hydroxyl value 160 mg KOH / g, heat loss at 270°C: 6.2%) was used.

[0210] (D-2) Terpene-based resin (manufactured by Yasuhara Chemical Co., Ltd., "Cryalon M105 (trade name)", acid value 0 mg KOH / g, loss of heat at 270°C: 7.5%) was used.

[0211] (D-3) Petroleum resin (Imabe P-100, manufactured by Idemitsu Kosan Co., Ltd., with hydroxyl value and acid value both below 1 mg KOH / g, and heat loss at 270°C: 7.0%) was used.

[0212] (Example 1) Using a long fiber reinforced resin granule manufacturing apparatus, the extruder barrel temperature was set to 260°C, and the aforementioned thermoplastic resin (B-1) was supplied from the main feed hopper and melt-mixed at a screw speed of 200 rpm. This long fiber reinforced resin granule manufacturing apparatus is equipped with a coating die for wire coating installed at the front end of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D=32) manufactured by Nippon Steel Works. Rosin resin (C-1), which had been heated and melted at 200°C, was adjusted in output to be 4 parts by weight relative to a total of 100 parts by weight of (A) to (C), and then fed into a fiber bundle composed of carbon fibers (A-1). This was then supplied to a die opening (3 mm in diameter) that would expel molten thermoplastic resin (B-1), continuously arranged around the carbon fibers (A-1). At this time, the internal cross-section of the fiber bundle ensures that at least a portion of the carbon fibers (A-1) is in contact with the thermoplastic resin (B-1). After cooling, the resulting bundles were cut into 7mm long granules using a cutting machine, producing long fiber granules. At this point, the receiving speed was adjusted so that carbon fiber (A-1) comprised 20 parts by weight of the total 100 parts by weight of the (A) to (C) series. The length of carbon fiber (A-1) in the obtained long fiber granules was substantially the same as the length of the granules.

[0213] Using an injection molding machine (J110AD manufactured by Nippon Steel Works), long-fiber granules obtained in the above process were injection molded 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: 60°C. ISO-type dumbbell-shaped test pieces, 80 mm × 80 mm × 3 mm thick test pieces for color evaluation and dispersion evaluation were produced. 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 used to inject resin into the specified shape. The obtained test pieces (molded products) were placed in a constant temperature and humidity chamber adjusted to 23°C and 50%RH for 24 hours before being submitted for characteristic evaluation. The evaluation results obtained by the aforementioned method are summarized and shown in Table 1.

[0214] (Examples 2-9) Except for changes in the composition ratio or the type of rosin resin used as described in Table 1, the molded articles were prepared in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Table 1.

[0215] (Examples 10-18) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Tables 1 and 2, and setting the barrel temperature to 230°C, the molded articles were produced in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Tables 1 and 2.

[0216] (Example 19) Except for changing the molding back pressure during injection molding to 20 MPa, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and shown in Table 2.

[0217] (Example 20) Except for changing the molding back pressure during injection molding to 15 MPa, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and shown in Table 2.

[0218] (Example 21) Except for changing the molding back pressure during injection molding to 3 MPa, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and shown in Table 2.

[0219] (Example 22) Except for changing the molding back pressure during injection molding to 1 MPa, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and shown in Table 2.

[0220] (Examples 23 and 24) Using a long fiber reinforced resin granule manufacturing apparatus, the extruder barrel temperature was set to 260°C, and the aforementioned thermoplastic resin (B-1) was supplied from the main feed hopper and melt-mixed at a screw speed of 200 rpm. This long fiber reinforced resin granule manufacturing apparatus is equipped with a coating die for wire coating installed at the front end of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D=32) manufactured by Nippon Steel Works. Rosin resin (C-2), which had been heated and melted at 200°C, was adjusted in output to be 4 parts by weight relative to a total of 100 parts by weight of (A) to (C), and then fed into a fiber bundle composed of carbon fiber (A-1) and organic fiber (A-2). This was then fed into a die orifice (3 mm in diameter) that would expel molten thermoplastic resin (B-1), continuously distributing it to coat the area around the carbon fiber (A-1) and organic fiber (A-2). At this point, the internal cross-section of the composite fiber bundle (E) shows a non-uniform distribution of carbon fiber (A-1) and organic fiber (A-2). This non-uniform distribution means that at least a portion of the carbon fiber (A-1) and organic fiber (A-2) are in contact with the thermoplastic resin (B-1). After cooling, the resulting bundle is cut into 7mm long granules using a cutting machine, producing long fiber granules. The receiving speed is adjusted so that the carbon fiber (A-1) is 20 parts by weight relative to the total 100 parts by weight of (A) to (C). The lengths of the carbon fiber (A-1) and organic fiber (A-2) in the obtained long fiber granules are substantially the same as the granule length. Except for producing long fiber granules, molded articles were manufactured in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and shown in Table 2.

[0221] (Examples 25 and 26) Except for changes in the composition ratio or the type of fiber used as described in Table 3, the molded articles were produced in the same manner as in Example 23, and evaluations were conducted. The evaluation results are summarized and recorded in Table 3.

[0222] (Examples 27 and 34) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, and setting the barrel temperature to 240°C, the molded articles were produced in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Table 3.

[0223] (Examples 28 and 35) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, and setting the barrel temperature to 270°C and the mold temperature to 80°C, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and recorded in Table 3.

[0224] (Example 29) Except for changes in the composition ratio or the type of resin and rosin resin used, as described in Table 3, and setting the barrel temperature to 330°C and the mold temperature to 140°C, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and recorded in Table 3.

[0225] (Example 30) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, and setting the barrel temperature to 280°C and the mold temperature to 100°C, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and recorded in Table 3.

[0226] (Example 31) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, and setting the barrel temperature to 200°C, the molded articles were produced in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Table 3.

[0227] (Example 32) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, and setting the barrel temperature to 320°C and the mold temperature to 130°C, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are summarized and recorded in Table 3.

[0228] (Example 33) Except for changes in the composition ratio or the type of rosin resin used as described in Table 3, the molded articles were prepared in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Table 3.

[0229] (Example 36) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 3, the molded articles were prepared in the same manner as in Example 10, and evaluations were conducted. The evaluation results are summarized and recorded in Table 3.

[0230] (Example 37) Using a long fiber reinforced resin granule manufacturing apparatus, the extruder barrel temperature was set to 270°C, and the aforementioned thermoplastic resin (Ba-1) and reactive functional group resin (Bb-1) were supplied from the main feed hopper and melt-blended at a screw speed of 200 rpm. This long fiber reinforced resin granule manufacturing apparatus is equipped with a coating die for wire coating installed at the front end of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D=32) manufactured by Nippon Steel Works. Rosin resin (C-1), which had been heated and melted at 200°C, was adjusted to produce 4 parts by weight relative to a total of 100 parts by weight of (A) to (C), and then fed into a fiber bundle composed of carbon fibers (A-1). This was then fed into a die orifice (3 mm in diameter) that extrudes molten thermoplastic resin (Ba-1) and reactive functional group resin (Bb-1), continuously distributing the mixture around the carbon fibers (A-1). At this point, the internal cross-section of the fiber bundle, consisting of at least a portion of the carbon fiber (A-1), is in contact with the thermoplastic resin (Ba-1) and the resin with reactive functional groups (Bb-1). After cooling, the resulting bundle is cut into 7mm long granules using a cutting machine, producing long fiber granules. The receiving speed is then adjusted so that the carbon fiber (A-1) comprises 20 parts by weight relative to the total 100 parts by weight of the (A)~(C) system. The length of the carbon fiber (A-1) in the obtained long fiber granules is substantially the same as the granule length.

[0231] Using an injection molding machine (J110AD manufactured by Nippon Steel Works), long-fiber granules obtained in the above process were injection molded under the following conditions: injection time: 2 seconds, back pressure: 5 MPa, holding pressure: 40 MPa, holding time: 10 seconds, barrel temperature: 270°C, and mold temperature: 80°C. ISO-type dumbbell-shaped test pieces, 80mm × 80mm × 3mm thick test pieces for color evaluation and dispersion evaluation were produced. 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 used to inject resin into the specified shape. The obtained test pieces (molded products) were placed in a constant temperature and humidity chamber adjusted to 23°C and 50%RH for 24 hours before being submitted for characteristic evaluation. The evaluation results obtained by the aforementioned method are summarized and shown in Table 4.

[0232] (Examples 38-47, 49, 50 and 59) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Tables 4 and 5, the molded articles were prepared in the same manner as in Example 37, and evaluations were conducted. The evaluation results are summarized and recorded in Tables 4 and 5.

[0233] (Example 48) Except for changes in the composition ratio or the type of resin and rosin resin used as described in Table 4, and setting the barrel temperature to 230°C and the mold temperature to 60°C, the molded articles were produced in the same manner as in Example 37, and the results were evaluated. The evaluation results are summarized and recorded in Table 4.

[0234] (Example 55) Except for changing the molding back pressure during injection molding to 20 MPa, the molded articles were produced in the same manner as in Example 37, and the results were evaluated. The evaluation results are summarized and shown in Table 5.

[0235] (Example 56) Except for changing the molding back pressure during injection molding to 15 MPa, the molded articles were produced in the same manner as in Example 37, and the results were evaluated. The evaluation results are summarized and shown in Table 5.

[0236] (Example 57) Except for changing the molding back pressure during injection molding to 3 MPa, the molded articles were produced in the same manner as in Example 37, and the results were evaluated. The evaluation results are summarized and shown in Table 5.

[0237] (Example 58) Except for changing the molding back pressure during injection molding to 1 MPa, the molded articles were produced in the same manner as in Example 37, and the results were evaluated. The evaluation results are summarized and shown in Table 5.

[0238] (Examples 51 and 52) Using a long fiber reinforced resin granule manufacturing apparatus, the extruder barrel temperature was set to 270°C. The aforementioned thermoplastic resin (Ba-1) and a resin with reactive functional groups (Bb-1) were supplied from the main feed hopper and melt-mixed at a screw speed of 200 rpm. This long fiber reinforced resin granule manufacturing apparatus was equipped with a coating die for wire coating installed at the front end of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D=32) manufactured by Nippon Steel Works. Rosin resin (C-2), which had been heated and melted at 200°C, was adjusted in output to be 4 parts by weight relative to a total of 100 parts by weight of (A) to (C). This was then fed into a fiber bundle composed of carbon fiber (A-1) and organic fiber (A-2) and supplied to a die orifice (3 mm in diameter) that would expel molten thermoplastic resin (B-1), continuously distributing it around the carbon fiber (A-1) and organic fiber (A-2). At this point, the internal cross-section of the composite fiber bundle (E) shows a non-uniform distribution of carbon fiber (A-1) and organic fiber (A-2). This non-uniform distribution means that at least a portion of the carbon fiber (A-1) and organic fiber (A-2) are in contact with the thermoplastic resin (Ba-1) and the resin with reactive functional groups (Bb-1). After cooling the obtained bundle, it is cut into 7mm long granules using a cutting machine to produce long fiber granules. At this point, the receiving speed is adjusted so that the carbon fiber (A-1) is 20 parts by weight relative to the total 100 parts by weight of (A) to (C). The lengths of the carbon fiber (A-1) and organic fiber (A-2) in the obtained long fiber granules are substantially the same as the granule length. Except for producing long fiber granules, molded articles were manufactured in the same manner as in Example 37, and evaluations were conducted. The evaluation results are summarized and shown in Table 5.

[0239] (Examples 53, 54 and 60) Except for changes in the composition ratio or the type of fiber and rosin resin used as described in Table 5, the molded articles were produced in the same manner as in Example 51, and evaluations were conducted. The evaluation results are summarized and recorded in Table 5.

[0240] (Comparative Examples 1-9) Except for changes in the composition ratio or the type of rosin resin used as described in Table 6, the molded articles were prepared in the same manner as in Example 1, and evaluations were conducted. The evaluation results are summarized and recorded in Table 6.

[0241] (Comparative Example 10) Except for changing the molding back pressure during injection molding to 40 MPa, the molded articles were produced in the same manner as in Example 1, and the results were evaluated. The evaluation results are shown in Table 6.

[0242] (Comparative Example 11) Except for changing the pellet length to 14 mm, the molded articles were produced in the same manner as in Example 4, and the results were evaluated. The evaluation results are shown in Table 6.

[0243] The materials in Examples 1-9 all exhibited excellent dispersibility and displayed high tensile strength, impact strength, and excellent appearance quality, particularly blackness. The materials in Examples 10-18 and 27-36, which varied the resin and rosin resin types, also showed excellent dispersibility and displayed high tensile strength, impact strength, and excellent appearance quality, particularly blackness. Even with variations in the fiber length in the molded articles, Examples 19-22 similarly demonstrated excellent results. Examples 23-26, which contained organic fibers (A-2) or glass fibers (A-3), also exhibited excellent results and further demonstrated excellent impact strength.

[0244] The materials in Examples 37-45 all exhibited excellent dispersibility and displayed high mechanical strength, particularly impact strength, and excellent appearance quality, especially blackness. The materials in Examples 46-50 and 59, which varied the resin and rosin resin types, also exhibited excellent dispersibility and displayed high mechanical strength, particularly impact strength, and excellent appearance quality, especially blackness. Even with variations in the fiber length in the molded articles, Examples 55-58 similarly demonstrated excellent results. Examples 51-54 and 60, which contained organic fibers (A-2) or glass fibers (A-3), also similarly exhibited excellent results and further demonstrated excellent impact strength.

[0245] On the other hand, in Comparative Examples 1-3, due to the absence of rosin resin, fiber entanglement occurred, resulting in insufficient dispersibility, and consequently, poor tensile strength, impact strength, appearance quality, and especially poor blackness. In Comparative Examples 4 and 5, due to the low hydroxyl value of the rosin resin, fiber entanglement occurred, resulting in insufficient dispersibility, and consequently, poor tensile strength, impact strength, appearance quality, and especially poor blackness.

[0246] In Comparative Example 6, the lack of reinforcing fibers resulted in weak fiber reinforcement, leading to poor tensile and impact strength. In Comparative Example 7, the excessive amount of reinforcing fibers caused them to become entangled and break within the molded article, resulting in insufficient dispersibility and poor impact strength. In Comparative Example 8, the low amount of rosin resin relative to the reinforcing fibers resulted in insufficient wettability between the reinforcing fibers and the thermoplastic resin, leading to poor tensile strength, impact strength, and appearance quality, particularly blackness. In Comparative Example 9, the excessive amount of rosin resin reduced the strength and toughness of the thermoplastic resin, resulting in poor tensile and impact strength of the molded article. In Comparative Example 10, the short length of the reinforcing fibers resulted in weak fiber reinforcement, leading to poor tensile and impact strength. In Comparative Example 11, the excessively long granules (i.e., excessively long fibers) resulted in insufficient dispersibility, leading to poor appearance quality, particularly blackness.

[0247] [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 Reinforced Fibers (A) Dosage weight 20.0 5.0 10.0 20.0 30.0 50.0 20.0 20.0 20.0 5.0 10.0 20.0 Fiber types - A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) or (A3) weight 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) or (A3) weight - - - - - - - - - - - - Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A2) or (A3) weight - - - - - - - - - - - - thermoplastic resin (B) type - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-4 B-4 B-4 Dosage weight 76.0 94.0 88.0 76.0 64.0 40.0 76.0 79.8 70.0 94.0 88.0 76.0 rosin resin (C) type - C-1 C-2 C-2 C-2 C-2 C-2 C-3 C-3 C-3 C-3 C-3 C-3 Acid value or hydroxyl value mgKOH / g 100.0 150.0 150.0 150.0 150.0 150.0 200.0 150.0 150.0 200.0 200.0 200.0 Rosin resin (C) at 270℃ Loss of heat % A A A A A A A A A A A A Dosage weight 4.0 1.0 2.0 4.0 6.0 10.0 4.0 0.2 10.0 1.0 2.0 4.0 Compared to reinforcing fiber (A) Rosin resin (C) content % 20.0 20.0 20.0 20.0 20.0 20.0 20.0 1.0 50.0 20.0 20.0 20.0 Molded products Average fiber length Lwa1 mm 1.2 1.7 1.5 1.2 1.0 0.4 1.2 1.0 1.3 1.2 1.2 1.2 Lwa2 mm - - - - - - - - - - - - Lwa3 mm - - - - - - - - - - - - Evaluation results Mechanical properties Charpy impact strength kJ / m2 15.0 9.0 11.0 17.0 21.0 25.0 14.0 12.0 15.0 12.0 15.0 16.0 Tensile strength MPa 240.0 160.0 220.0 270.0 290.0 300.0 250.0 220.0 250.0 155.0 170.0 200.0 Bending Modulus GPa 15.0 5.0 10.0 15.0 20.0 35.0 15.0 15.0 15.0 4.0 10.0 13.0 Appearance quality Dispersion - A A A A A B A B A A A A Blackness - A A A A A B A B A A A A

[0248] [Table 2] Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 raw material Reinforcing fiber (A) Dosage weight 30.0 5.0 10.0 20.0 30.0 20.0 20.0 20.0 20.0 20.0 25.0 15.0 Fiber types - A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 / A-2 A-1 / A-2 Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) or (A3) weight 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 80.0 70.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) or (A3) weight - - - - - - - - - - 20.0 30.0 Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A2) or (A3) weight - - - - - - - - - - - - Thermoplastic resin (B) type - B-4 B-4 B-4 B-4 B-4 B-4 B-1 B-1 B-1 B-1 B-1 B-1 Dosage weight 64.0 94.0 88.0 76.0 64.0 76.0 76.0 76.0 76.0 76.0 70.0 82.0 rosin resin (C) type - C-3 C-2 C-2 C-2 C-2 C-3 C-2 C-2 C-2 C-2 C-2 C-2 Acid value or hydroxyl value mgKOH / g 200.0 150.0 150.0 150.0 150.0 200.0 150.0 150.0 150.0 150.0 150.0 150.0 Rosin resin (C) at 270℃ Loss of heat % A A A A A A A A A A A A Dosage weight 6.0 1.0 2.0 4.0 6.0 4.0 4.0 4.0 4.0 4.0 5.0 3.0 Compared to reinforcing fiber (A) Rosin resin (C) content % 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Molded products Average fiber length Lwa1 mm 1.0 1.7 1.5 1.2 1.0 1.2 0.1 2.5 4.0 7.0 1.2 1.4 Lwa2 mm - - - - - - - - - - 5.5 6.0 Lwa3 mm - - - - - - - - - - - - Evaluation results Mechanical properties Charpy impact strength kJ / m2 18.0 13.0 15.0 17.0 19.0 14.0 10.0 18.0 21.0 30.0 27.0 20.0 Tensile strength MPa 245.0 160.0 180.0 210.0 250.0 190.0 180.0 270.0 275.0 280.0 230.0 190.0 Bending Modulus GPa 19.0 4.0 10.0 14.0 19.0 14.0 13.0 15.0 15.0 17.0 14.0 9.0 Appearance quality Dispersion - A A A A A A A A A A A A Blackness - A A A A A A A A A A A A

[0249] [Table 3] Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 raw material Reinforced Fibers (A) Dosage weight 25.0 15.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Fiber types - A-1 / A-3 A-1 / A-3 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) or (A3) weight 80.0 70.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) or (A3) weight - - - - - - - - - - - - Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A2) or (A3) weight 20.0 30.0 - - - - - - - - - - thermoplastic resin (B) type - B-1 B-1 B-2 B-3 B-5 B-6 B-7 B-8 B-1 B-2 B-3 B-4 Dosage weight 71.0 81.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 rosin resin (C) type - C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-4 C-4 C-4 C-4 Acid value or hydroxyl value mgKOH / g 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0 230.0 230.0 230.0 230.0 Rosin resin (C) at 270℃ Loss of heat % A A A A A A A A B B B B Dosage weight 5.0 3.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Compared to reinforcing fibers (A) Rosin resin (C) content % 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Molded products Average fiber length Lwa1 mm 1.2 1.4 1.0 1.1 1.0 1.4 1.3 0.8 1.3 1.2 1.2 1.2 Lwa2 mm - - - - - - - - - - - - Lwa3 mm 2.0 2.5 - - - - - - - - - - Evaluation results Mechanical properties Charpy impact strength kJ / m2 22.0 15.0 18.0 25.0 15.0 10.0 15.0 12.0 13.0 16.0 20.0 14.0 Tensile strength MPa 240.0 200.0 220.0 200.0 320.0 160.0 190.0 245.0 250.0 240.0 230.0 220.0 Bending Modulus GPa 16.0 11.0 16.0 15.0 22.0 11.0 16.0 17.0 15.0 16.0 14.0 14.0 Appearance quality Dispersion - A A A A A B A A B B B B Blackness - A A A A A B A A B B B B

[0250] [Table 4] Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 raw material Reinforced Fibers (A) Dosage weight 20.0 5.0 10.0 20.0 30.0 5.0 10.0 20.0 30.0 20.0 20.0 20.0 Fiber types - A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) weight 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) weight - - - - - - - - - - - - Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A3) weight - - - - - - - - - - - - Melt blending Resin composition (B1) (Ba) type - Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-2 (Bb) categories - Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-2 Bb-3 Bb-1 Dosage weight 76.0 94.0 88.0 76.0 64.0 94.0 88.0 76.0 64.0 76.0 76.0 76.0 rosin resin (C) type - C-1 C-2 C-2 C-2 C-2 C-3 C-3 C-3 C-3 C-2 C-2 C-2 Acid value or hydroxyl value mgKOH / g 100.0 150.0 150.0 150.0 150.0 200.0 200.0 200.0 200.0 150.0 150.0 150.0 Rosin resin (C) at 270℃ Loss of heat % A A A A A A A A A A A A Dosage weight 4.0 1.0 2.0 4.0 6.0 1.0 2.0 4.0 6.0 4.0 4.0 4.0 Compared to reinforcing fiber (A) Rosin resin (C) content % 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Molded products Average fiber length Lwa1 mm 1.0 1.5 1.2 1.0 0.8 1.5 1.2 1.0 0.8 0.9 1.0 1.1 Lwa2 mm - - - - - - - - - - - - Lwa3 mm - - - - - - - - - - - - morphology The particle size of (Bb) is 10~1000 nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ (Bc) has a particle size of 1~100nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ (Bc) in (Bb) Area ratio of 20% or more - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Evaluation results Mechanical properties Charpy impact strength kJ / m2 22.0 14.0 16.0 25.0 31.0 12.0 15.0 21.0 25.0 23.0 24.0 24.0 Tensile strength MPa 190.0 130.0 175.0 215.0 230.0 100.0 140.0 200.0 185.0 205.0 200.0 200.0 Bending Modulus GPa 12.0 4.0 8.0 12.0 16.0 3.0 7.0 12.0 13.0 12.0 12.0 13.0 Appearance quality Dispersion - A A A A A A A A A A A A Blackness mm A A A A A A A A A A A A

[0251] [Table 5] Example 49 Example 50 Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 Example 57 Example 58 Example 59 Example 60 raw material Reinforced Fibers (A) Dosage weight 20.0 20.0 25.0 15.0 25.0 15.0 20.0 20.0 20.0 20.0 20.0 25.0 Fiber types - A1 A1 A1 / A2 A1 / A2 A1 / A3 A1 / A3 A1 A1 A1 A1 A1 A1 / A2 Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) weight 100.0 100.0 80.0 70.0 80.0 70.0 100.0 100.0 100.0 100.0 100.0 80.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) weight - - 20.0 30.0 - - - - - - - 20.0 Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A3) weight - - - - 20.0 30.0 - - - - - - Melt blending resin composition (B1) (Ba) type - Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 (Bb) categories - Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Dosage weight 79.8 70.0 70.0 82.0 70.0 82.0 76.0 79.8 70.0 79.0 76.0 70.0 rosin resin (C) type - C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-2 C-4 C-4 Acid value or hydroxyl value mgKOH / g 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0 150.0 230.0 230.0 Rosin resin (C) at 270℃ Loss of heat % A A A A A A A A A A B B Dosage weight 0.2 10.0 5.0 3.0 5.0 3.0 4.0 0.2 10.0 1.0 4.0 5.0 Compared to reinforcing fiber (A) Rosin resin (C) content % 1.0 50.0 20.0 20.0 20.0 20.0 20.0 1.0 50.0 5.0 20.0 20.0 Molded products Average fiber length Lwa1 mm 1.0 1.4 1.1 1.2 1.1 1.3 0.1 2.5 4.0 7.0 1.0 1.1 Lwa2 mm - - 5.0 5.7 - - - - - - - 4.5 Lwa3 mm - - - - 2.2 2.1 - - - - - - morphology The particle size of (Bb) is 10~1000 nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ (Bc) has a particle size of 1~100nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The area ratio of (Bc) in (Bb) is: More than 20% - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Evaluation results Mechanical properties Charpy impact strength kJ / m2 22.0 25.0 40.5 30.0 33.0 22.5 15.0 27.0 31.0 45.0 20.0 30.0 Tensile strength MPa 190.0 210.0 180.0 180.0 210.0 195.0 150.0 215.0 220.0 230.0 200.0 170.0 Bending Modulus GPa 12.0 12.0 12.0 4.0 13.0 5.0 11.0 12.0 12.0 14.0 12.0 12.0 Appearance quality Dispersion - B A A A A A A A A A B B Blackness mm B A A A A A A A A A B B

[0252] [Table 6] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 raw material Reinforced Fibers (A) Dosage weight 20.0 20.0 20.0 20.0 20.0 1.0 60.0 20.0 20.0 20.0 20.0 Fiber types - CF CF CF CF CF CF CF CF CF CF CF Relative to a total of 100 parts by weight (A1) The amount of (A1) mixed with (A2) or (A3) weight 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Relative to a total of 100 parts by weight (A1) The amount of (A2) blended with (A2) or (A3) weight - - - - - - - - - - - Relative to a total of 100 parts by weight (A1) The amount of (A3) blended with (A2) or (A3) weight - - - - - - - - - - - Melt blending resin composition (B1) (Ba) type - Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 Ba-1 (Bb) categories - Bb-1 Bb-1 - Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Bb-1 Dosage weight 76.0 76.0 76.0 76.0 76.0 98.8 29.0 79.9 40.0 76.0 76.0 rosin resin (C) type - - - - C-5 C-6 C-2 C-2 C-2 C-2 C-2 C-2 Acid value or hydroxyl value mgKOH / g - - - 50.0 80.0 150.0 150.0 150.0 150.0 150.0 150.0 Loss of heat on rosin resin (C) at 270°C % - - - A A A A A A A A Dosage weight - - - 4.0 4.0 0.2 11.0 0.1 40.0 4.0 4.0 Compared to reinforcing fiber (A) Rosin resin (C) content % - - - 20.0 20.0 20.0 18.3 0.5 200.0 20.0 20.0 resin (D) type - D-1 D-2 D-3 - - - - - - - - Acid value or hydroxyl value mgKOH / g 160.0 0.0 1.0 - - - - - - - - Resin (D) at 270℃ Loss of heat % B C C - - - - - - - - Dosage weight 4.0 4.0 4.0 - - - - - - - - Compared to reinforcing fiber (A) Resin (D) content % 20.0 20.0 20.0 - - - - - - - - Molded products Average fiber length Lwa1 mm 1.0 0.9 0.8 0.8 0.8 1.5 0.1 0.6 1.3 0.05 10.0 Lwa2 mm - - - - - - - - - - - Lwa3 mm - - - - - - - - - - - morphology The particle size of (Bb) is 10~1000 nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ (Bc) has a particle size of 1~100nm. - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The area ratio of (Bc) in (Bb) is: More than 20% - ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Evaluation results Mechanical properties Charpy impact strength kJ / m2 10.0 9.0 9.0 9.0 9.0 6.0 20.0 8.0 9.0 7.0 9.0 Tensile strength MPa 150.0 140.0 140.0 150.0 155.0 50.0 210.0 145.0 160.0 140.0 150.0 Bending Modulus GPa 9.0 9.0 9.0 9.0 9.0 2.0 31.0 9.0 9.0 7.0 8.0 Appearance quality Dispersion - C C C C C A C A B A C Blackness - C C C C C C A A B A C [Potential for industrial application]

[0253] The fiber-reinforced thermoplastic resin composition of the present invention has excellent tensile strength, impact strength and appearance quality, and is therefore suitable for use in electrical / electronic machines, OA machines, home appliances, frames, moving parts and automotive parts.

[0254] 1: Reinforcing Fiber (A) 2: Thermoplastic resin (B) 3: Rosin Resin (C) 4: Fiber bundle

Claims

1. A fiber-reinforced thermoplastic resin composition comprising: 5 to 50 parts by weight of reinforcing fiber (A) containing at least carbon fiber, 20 to 94.5 parts by weight of thermoplastic resin (B), and 0.5 to 30 parts by weight of rosin resin (C), wherein the rosin resin (C) has an acid value and / or hydroxyl value of 100 mg KOH / g or higher, and the rosin resin (C) has a heat loss of less than 5% at 270°C.

2. The fiber-reinforced thermoplastic resin composition of claim 1, wherein the fiber-reinforced thermoplastic resin composition contains 1 to 100 parts by weight of rosin resin (C) relative to 100 parts by weight of the reinforcing fiber (A).

3. The fiber-reinforced thermoplastic resin composition of claim 1, wherein the rosin resin (C) is modified.

4. The fiber-reinforced thermoplastic resin composition of claim 1, wherein the rosin resin (C) comprises at least one selected from the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin esters and rosin polyols.

5. The fiber-reinforced thermoplastic resin composition of claim 1, wherein the reinforcing fiber (A) further comprises at least one selected from the group consisting of organic fibers and glass fibers.

6. The fiber-reinforced thermoplastic resin composition of claim 5, wherein the organic fiber is selected from at least one of the group consisting of polyamide fiber, polyester fiber, liquid crystal polyester fiber, polyarylate sulfide fiber and fluoropolymer fiber.

7. A fiber-reinforced thermoplastic resin composition as claimed in any of claims 1 to 6, wherein the weight-average fiber length (Lw) of the reinforcing fiber (A) is 0.1 to 7.0 mm.

8. The fiber-reinforced thermoplastic resin composition of claim 7, wherein the thermoplastic resin (B) comprises at least one selected from the group consisting of polyamide resins, polyolefin resins, polycarbonate resins and polyphenylene sulfide resins.

9. The fiber-reinforced thermoplastic resin composition of claim 7, wherein the thermoplastic resin (B) comprises at least two different thermoplastic resins (Ba) and (Bb).

10. The fiber-reinforced thermoplastic resin composition of claim 9, comprising 20 to 94.5 parts by weight of a melt-blended resin composition (B1) obtained by melt-blending thermoplastic resin (Ba) and thermoplastic resin (Bb), wherein the thermoplastic resin (Bb) comprises a thermoplastic resin having reactive functional groups; the melt-blended resin composition (B1) comprises: thermoplastic resin (Ba) and resin (Bb) having reactive functional groups, and a compound (Bc) generated by the reaction of resin (Ba) and resin (Bb), and the melt-blended resin composition (B1) comprises resin (Bb) having reactive functional groups dispersed in the thermoplastic resin (Ba) in a particulate form with a number average particle size of 10 to 1,000 nm.

11. The fiber-reinforced thermoplastic resin composition of claim 10, wherein the thermoplastic resin (Ba) contained in the melt-blended resin composition (B1) forms a continuous phase, the resin (Bb) having reactive functional groups forms a dispersed phase, and the dispersed phase contains microparticles with a particle size of 1 to 100 nm containing the compound (Bc).

12. The fiber-reinforced thermoplastic resin composition of claim 11, wherein the microparticles containing the compound (Bc) occupy an area ratio of 20% or more in the dispersed phase containing the resin (Bb).

13. The fiber-reinforced thermoplastic resin composition of claim 10, wherein the reactive functional group of the resin (Bb) is selected from at least one of amine, carboxyl, metal salt of carboxyl, epoxy, acid anhydride and zoline.

14. The fiber-reinforced thermoplastic resin composition of claim 9, wherein the thermoplastic resin (Ba) is a polyamide resin and the resin (Bb) is a polyolefin resin.

15. The fiber-reinforced thermoplastic resin composition of claim 1, wherein the rosin resin (C) is a reaction product of hydrogenated rosin or disproportionated rosin and epoxy resin.

16. A molding material comprising a fiber-reinforced thermoplastic resin composition as claimed in claim 1.

17. The molding material of claim 16, wherein a thermoplastic resin (B) is disposed on the outside of a composite filled with rosin resin (C) between the individual fibers of the fiber bundle, wherein the fiber bundle includes reinforcing fibers (A).

Images