Fiber-reinforced thermoplastic resin composition

Abstract

A fiber-reinforced thermoplastic resin composition comprising 5-50 parts by weight of reinforcing fibers (A) at least including carbon fibers, 20-94.5 parts by weight of a thermoplastic resin (B), and 0.5-30 parts by weight of a rosin resin (C), wherein the rosin resin (C) has an acid value of 100 mgKOH / g or greater and / or a hydroxyl value of 100 mgKOH / g or greater. Due to the inclusion of both the reinforcing fibers at least including carbon fibers and the specific rosin resin, this fiber-reinforced thermoplastic resin composition has the high reinforcing effect of the reinforcing fibers and can give molded fiber-reinforced thermoplastic resin articles excellent in terms of tensile strength, impact strength, and appearance quality, particularly blackness.

Description

Fiber-reinforced thermoplastic resin composition

[0001] The present invention relates to a fiber-reinforced thermoplastic resin composition containing at least carbon fibers and a rosin resin.

[0002] Molded articles containing reinforcing fibers and thermoplastic resins are lightweight and have excellent mechanical properties, and are therefore widely used in sporting goods, aerospace, general industrial applications, etc. These reinforcing fibers include metal fibers such as aluminum fibers and stainless steel fibers, inorganic fibers such as silicon carbide fibers and carbon fibers, and organic fibers such as aramid fibers and polyparaphenylenebenzoxazole (PBO) fibers. However, carbon fibers are preferred from the viewpoint of the balance between specific strength, specific rigidity, and light weight, and among these, polyacrylonitrile (PAN)-based carbon fibers are preferred.

[0003] Reinforcing fibers have an excellent reinforcing effect when combined with a thermoplastic resin, but to enhance this effect, the reinforcing fibers must be uniformly dispersed in a thermoplastic resin molded product. If the reinforcing fibers remain in a non-uniform state, i.e., in the form of fiber bundles, a decrease in tensile strength and impact strength is observed. Therefore, when used as a structural member requiring strength, a sufficient reinforcing effect cannot be obtained, and there is a risk of breakage during actual use. Furthermore, non-uniform fiber dispersion can cause defects such as color unevenness in the appearance of the molded product. For these reasons, there is a demand for a fiber-reinforced thermoplastic resin composition that has excellent tensile strength, impact strength, and appearance quality.

[0004] As a means for improving the mechanical properties and appearance quality of fiber-reinforced thermoplastic resin molded articles, for example, a method using a terpene-based resin as the reinforcing fiber and thermoplastic resin has been proposed (e.g., Patent Document 1). Furthermore, as a means for enhancing the reinforcing effect of concrete members, a method for compounding reinforcing fibers with concrete or mortar has been proposed (e.g., Patent Document 2). Furthermore, as a means for improving the adhesiveness of thermoplastic resins, a modified polypropylene resin in which a rosin resin has been added to the thermoplastic resin has been proposed (e.g., Patent Document 3). As a means for improving the impact resistance of fiber-reinforced thermoplastic resin molded articles, for example, a method for using a terpene-based resin in a melt-kneaded mixture consisting of reinforcing fibers, a thermoplastic resin, and a resin having a reactive functional group has been proposed (e.g., Patent Document 4). Furthermore, a method for improving impact resistance by using organic fibers in addition to carbon fibers has been proposed (e.g., Patent Document 5). However, molded articles obtained using these techniques have had problems such as insufficient fiber dispersion of the reinforcing fibers in the fiber-reinforced thermoplastic resin molded articles, resulting in insufficient tensile strength, impact strength, and appearance quality, particularly blackness.

[0005] As described above, in the prior art, fiber-reinforced thermoplastic resin molded articles having high tensile strength, impact properties, and good appearance quality have not been obtained in fiber-reinforced thermoplastic resin molded articles using a thermoplastic resin as a matrix, and there has been a demand for the development of such a fiber-reinforced thermoplastic resin composition.

[0006] Japanese Patent Application Laid-Open No. 10-138379 Japanese Patent Application Laid-Open No. 2011-162905 Japanese Patent Application Laid-Open No. 2016-74866 International Publication No. 2010 / 107022 International Publication No. 2014 / 098103

[0007] In view of the above problems of the prior art, the present invention provides a fiber-reinforced thermoplastic resin composition capable of obtaining a fiber-reinforced thermoplastic resin molded product excellent in tensile strength, impact strength and appearance quality, particularly blackness. An object of the present invention is to provide a fiber-reinforced thermoplastic resin composition.

[0008] In order to solve the above problems, the present invention mainly has the following configurations. (1) A fiber-reinforced thermoplastic resin composition containing 5 to 50 parts by weight of reinforcing fibers (A) including at least carbon fibers, 20 to 94.5 parts by weight of a thermoplastic resin (B), and 0.5 to 30 parts by weight of a rosin resin (C), wherein the rosin resin (C) has an acid value and / or a hydroxyl value of 100 mgKOH / g or more. (2) The fiber-reinforced thermoplastic resin composition according to (1), containing 1 to 100 parts by weight of the rosin resin (C) per 100 parts by weight of the reinforcing fibers (A). (3) The fiber-reinforced thermoplastic resin composition according to (1) or (2), wherein the rosin resin (C) is modified. (4) The fiber-reinforced thermoplastic resin composition according to any one of (1) to (3), wherein the 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 according to any one of (1) to (4), wherein the rosin resin (C) has a heat loss of less than 5% at 270°C. (6) The fiber-reinforced thermoplastic resin composition according to any one of (1) to (5), wherein the reinforcing fiber (A) further comprises at least one fiber selected from the group consisting of organic fibers and glass fibers. (7) The fiber-reinforced thermoplastic resin composition according to (6), wherein the organic fiber is at least one fiber selected from the group consisting of polyamide fibers, polyester fibers, liquid crystal polyester fibers, polyarylene sulfide fibers, and fluororesin fibers. (8) The fiber-reinforced thermoplastic resin composition according to any one of (1) to (7), wherein the reinforcing fiber (A) has a weight-average fiber length (Lw) of 0.1 to 7.0 mm. (9) The fiber-reinforced thermoplastic resin composition according to any one of (1) to (8), 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. (10) The fiber-reinforced thermoplastic resin composition according to any one of (1) to (9), wherein the thermoplastic resin (B) is composed of at least two different thermoplastic resins (Ba) and (Bb).(11) The thermoplastic resin (Bb) is a thermoplastic resin having a reactive functional group, and contains 20 to 94.5 parts by weight of a melt-kneaded resin composition (B1) obtained by melt-kneading the thermoplastic resin (Ba) and the thermoplastic resin (Bb). The melt-kneaded resin composition (B1) contains a thermoplastic resin (Ba) and a resin (Bb) having a reactive functional group. The melt-kneaded resin composition (B1) contains a compound (Bc) produced by the reaction of the resin (Ba) and the resin (Bb), and the melt-kneaded resin composition (B1) is a fiber-reinforced thermoplastic resin composition according to (10), in which the resin (Bb) having a reactive functional group in the thermoplastic resin (Ba) is dispersed in the form of particles with a number average particle diameter of 10 to 1,000 nm. (12) The fiber-reinforced thermoplastic resin composition according to (11), wherein the thermoplastic resin (Ba) contained in the melt-kneaded resin composition (B1) forms a continuous phase, and the resin (Bb) having a reactive functional group forms a dispersed phase, and the dispersed phase contains fine particles of compound (Bc) having a particle diameter of 1 to 100 nm. (13) The fiber-reinforced thermoplastic resin composition according to (12), wherein the fine particles of compound (Bc) account for 20% or more of the area of ​​the dispersed phase of resin (Bb). (14) The fiber-reinforced thermoplastic resin composition according to any one of (11) to (13), wherein the reactive functional group of resin (Bb) is at least one selected from an amino group, a carboxyl group, a metal salt of a carboxyl group, an epoxy group, an acid anhydride group, and an oxazoline group. (15) The fiber-reinforced thermoplastic resin composition according to any one of (10) to (14), wherein the thermoplastic resin (Ba) is a polyamide resin, and resin (Bb) is a polyolefin resin.

[0009] The fiber-reinforced thermoplastic resin composition of the present invention contains reinforcing fibers including at least carbon fibers and a rosin resin having an acid value and / or hydroxyl value of 100 mgKOH / g or more, and therefore has a high reinforcing effect due to the reinforcing fibers, and can provide a fiber-reinforced thermoplastic resin molded article that is excellent in tensile strength, impact strength, and appearance quality, particularly in blackness of the molded article. The fiber-reinforced thermoplastic resin composition of the present invention is extremely useful for electric and electronic devices, office automation equipment, home appliances, housings, sports components, automobile parts, etc.

[0010] Fig. 1 is a schematic diagram showing an example of a cross-sectional form of a fiber bundle in the present invention. Fig. 2 is a schematic diagram showing an example of a preferred longitudinal cross-sectional form of a molding material in the present invention. Fig. 3 is a schematic diagram showing an example of a preferred cross-sectional form of a molding material in the present invention. Fig. 4 is a schematic diagram showing another example of a preferred cross-sectional form of a molding material in the present invention.

[0011] The fiber-reinforced thermoplastic resin composition of the present invention (hereinafter, sometimes simply referred to as "composition") contains at least carbon fiber-containing reinforcing fibers (A), a thermoplastic resin (B), and a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more.

[0012] The reinforcing fibers (A) are preferably in the form of continuous reinforcing fiber bundles as a starting material, and as a reinforcing material, they impart high mechanical properties to molded articles. The thermoplastic resin (B) is a matrix resin with a relatively high viscosity and high physical properties, such as toughness, and serves to firmly hold the reinforcing fibers (A), including at least carbon fibers, in the molded article. The rosin resin (C) having an acid value and / or hydroxyl value of 100 mg KOH / g or more uniformly disperses the reinforcing fibers (A) in the thermoplastic resin (B), imparting excellent tensile strength and impact strength, as well as good appearance quality.

[0013] Compared with techniques for improving strength and appearance by adding a general compatibilizer or terpene resin, the inclusion of a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more can significantly improve tensile strength, impact strength, and appearance quality.

[0014] The molded article and composition of the present invention contain 5 to 50 parts by weight of reinforcing fiber (A) per 100 parts by weight of the total of reinforcing fiber (A), thermoplastic resin (B), and rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more. 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 the reinforcing fiber (A) in the molded article will decrease, often causing 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. There are no particular restrictions on the types of other fibers contained in the reinforcing fiber (A), but glass fiber and organic fiber are preferred as fibers with high reinforcing effects. Depending on the desired reinforcing effect, it is also preferable to use two or more of these reinforcing fibers in combination. In this case, the combination of reinforcing fibers is appropriately selected depending on the desired properties.

[0016] Examples of types of carbon fibers include PAN-based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, vapor-grown carbon fibers, and graphitized fibers thereof. PAN-based carbon fibers are carbon fibers made from polyacrylonitrile fibers. Pitch-based carbon fibers are carbon fibers made from petroleum tar or petroleum pitch. Cellulose-based carbon fibers are carbon fibers made from viscose rayon, cellulose acetate, or the like. Vapor-grown carbon fibers are carbon fibers made from hydrocarbons or the like. Of these, PAN-based carbon fibers are preferred because of their excellent balance between strength and elastic modulus. Furthermore, carbon fibers coated with metals such as nickel, copper, or ytterbium can also be used to further improve conductivity.

[0017] The surface oxygen concentration ratio [O / C] of the 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 carbon (C) atoms on the fiber surface measured by X-ray photoelectron spectroscopy. A surface oxygen concentration ratio of 0.05 or more can ensure a sufficient amount of functional groups on the carbon fiber surface, resulting in stronger adhesion, and thus further improving bending strength and tensile strength. 0.08 or more is more preferable, and 0.1 or more is even more preferable. There is no particular upper limit to the surface oxygen concentration ratio, but from the perspective of balancing the handleability and productivity of the carbon fiber, 0.5 or less is generally preferable. 0.4 or less is more preferable, and 0.3 or less is even more preferable.

[0018] The surface oxygen concentration ratio of carbon fibers is determined by X-ray photoelectron spectroscopy according to the following procedure: First, a carbon fiber bundle is removed with a solvent from the sizing agent and other materials adhering to the surface of the carbon fiber, and the bundle is cut into 20 mm pieces. The bundle is then spread out and arranged on a copper sample support. Then, an X-ray source is used, and a 1×10 －８ Torr. The kinetic energy (K.E.) of the main C1s peak is set to 1202 eV as a correction value for peaks associated with charging during measurement. The C1s peak area is determined as K.E. by drawing a straight baseline in the range of 1191 to 1205 eV. The O1s peak area is determined as K.E. by drawing a straight baseline in the range of 947 to 959 eV.

[0019] Here, the surface oxygen concentration ratio is calculated as an atomic ratio from the ratio of the O1s peak area to the C1s peak area using a sensitivity correction value specific to the device. The X-ray photoelectron spectrometer used is an ES-200 model manufactured by Kokusai Electric Co., Ltd., with a sensitivity correction value of 1.74.

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

[0021] The average fiber diameter of the carbon fiber is not particularly limited, but is preferably 1 to 20 μm, more preferably 3 to 15 μm, from the viewpoint of the mechanical properties and surface appearance of the molded article. The number of single fibers in the reinforcing fiber bundle is not particularly limited, but is preferably 100 to 350,000, and more preferably 20,000 to 100,000 from the viewpoint of productivity.

[0022] The carbon fibers may be surface-treated for the purpose of improving the adhesion between the carbon fibers and the thermoplastic resin (B) which is the matrix resin, etc. Examples of the surface treatment method include electrolysis, ozone treatment, and ultraviolet treatment.

[0023] The carbon fibers may be coated with a sizing agent for purposes such as preventing fuzzing of the carbon fibers and improving adhesion between the carbon fibers and the thermoplastic resin (B) that is the matrix resin. Specific examples of sizing agents include epoxy resins, phenolic resins, polyethylene glycol, polyurethane, polyester, emulsifiers, and surfactants. Two or more of these may be used. These sizing agents are contained on the surface of the carbon fibers in the molding material. The sizing agent is preferably water-soluble or water-dispersible, and an epoxy resin that has excellent wettability with the carbon fibers is preferred. Among these, a multifunctional epoxy resin is more preferred.

[0024] Examples of polyfunctional epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, aliphatic epoxy resins, and phenol novolac epoxy resins. Among these, aliphatic epoxy resins are preferred because they exhibit excellent adhesion to matrix resins. Aliphatic epoxy resins have a flexible backbone, which allows them to form highly tough structures even with high crosslinking densities. When present between carbon fiber and matrix resin, they are flexible and resist peeling, further improving the strength of molded articles. Examples of polyfunctional aliphatic epoxy resins include diglycidyl ether compounds such as ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ethers, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ethers. Examples of polyglycidyl ether compounds include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, trimethylolpropane glycidyl ethers, pentaerythritol polyglycidyl ethers, and polyglycidyl ethers of aliphatic polyhydric alcohols.

[0025] Among the above aliphatic epoxy resins, aliphatic polyglycidyl ether compounds having a large number of highly reactive glycidyl groups are more preferred. Aliphatic polyglycidyl ether compounds have a good balance of flexibility, crosslink density, and compatibility with the matrix resin, and can further improve adhesion. Among these, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ethers, and polypropylene glycol glycidyl ethers are more preferred.

[0026] The amount of sizing agent attached is preferably 0.01 parts by weight or more and 10 parts by weight or less relative to 100 parts by weight of carbon fiber. If the amount of sizing agent attached is 0.01 parts by weight or more, the adhesion to the thermoplastic resin (B) is further improved. 0.05 parts by weight or more is more preferable, and 0.1 parts by weight or more is even more preferable. 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. 5 parts by weight or less is more preferable, and 2 parts by weight or less is even more preferable.

[0027] The means for applying the sizing agent is not particularly limited, but examples include a method of immersing the carbon fibers in the sizing solution via a roller, a method of bringing the carbon fibers into contact with a roller to which the sizing solution is attached, and a method of spraying the sizing solution in a mist onto the carbon fibers. While either a batch method or a continuous method may be used, a continuous method is preferred because it provides good productivity and small variations. In this case, it is preferable to control the sizing solution concentration, temperature, yarn tension, etc. so that the amount of the active ingredient of the sizing agent attached to the carbon fibers is uniformly attached within an appropriate range. It is also more preferable to vibrate the carbon fibers with ultrasound when applying the sizing agent.

[0028] The drying temperature and drying time should be adjusted depending on the amount of the compound attached. From the viewpoints of completely removing the solvent used in applying the sizing agent, shortening the time required for drying, preventing thermal deterioration of the sizing agent, and preventing the sized carbon fiber from becoming hard and deteriorating in spreadability, the drying temperature is preferably 150° C. or higher and 350° C. or lower, and more preferably 180° C. or higher and 250° C. or lower.

[0029] Examples of solvents used to dilute the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylacetamide, and acetone. However, water is preferred from the standpoint of ease of handling and disaster prevention. Therefore, when using a water-insoluble or poorly soluble compound as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse it in water. Specifically, emulsifiers and surfactants that can be used include anionic emulsifiers such as styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, and sodium polyacrylate; cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline; and nonionic emulsifiers such as nonylphenol ethylene oxide adduct, polyvinyl alcohol, polyoxyethylene ether ester copolymer, and sorbitan ester ethyl oxide adduct. However, nonionic emulsifiers with low interaction are preferred because they are less likely to inhibit the adhesive effect of the polyfunctional compound.

[0030] The composition of the present invention may contain organic fibers or glass fibers in addition to the carbon fibers described above. Inorganic fibers such as carbon fibers are rigid and brittle, and therefore tangle and break easily. Therefore, fiber bundles consisting only of inorganic fibers have the problem of being easily broken during the production of molded articles or easily falling off from the molded articles. Therefore, by including organic fibers that are flexible and difficult to break and tend to bend in the molded article, the impact strength of the molded article can be significantly improved. In particular, the impact strength at low temperatures can be improved in addition to the impact strength at room temperature.

[0031] In the present invention, the content of organic fibers in the composition is preferably 1 to 45 parts by weight per 100 parts by weight of reinforcing fibers (A). If the content of organic fibers is less than 1 part by weight, the impact strength of the molded article will decrease. The content of organic fibers 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, if the content of organic fibers exceeds 45 parts by weight, entanglement between fibers will increase, the dispersibility of the organic fibers in the molded article will decrease, and this will often cause a decrease in the tensile strength, impact strength, and appearance quality of the molded article. The content of organic fibers 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 breaking elongation of the organic fiber used in the present invention is preferably 10 to 50%. When the tensile breaking elongation of the organic fiber is 10% or more, the impact strength of the molded article can be further improved, and 15% or more is more preferable. On the other hand, when the tensile breaking elongation of the organic fiber is 50% or less, the fiber strength and the rigidity of the molded article can be further improved, and 40% or less is more preferable.

[0033] The tensile breaking elongation (%) of an organic fiber can be determined by the following method. A tensile test is carried out in a room under standard conditions (20°C, 65% RH) under conditions of a gripping distance of 250 mm and a pulling speed of 300 mm / min, and the length at the time of fiber breakage is measured (however, if the fiber is broken near the chuck, this is considered a chuck break and is excluded from the data), and the result is calculated to two decimal places using the following formula, with the first decimal place rounded off. The average value of data n3 is determined and is defined as the tensile breaking elongation in the present invention. Tensile breaking elongation (%) = [(length at break (mm) - 250) / 250] x 100

[0034] The single fiber fineness of the organic fiber is preferably 0.1 to 10 dtex.

[0035] The organic fibers can be appropriately selected within a range that does not significantly reduce the mechanical properties of the molded article. Examples include fibers obtained by spinning polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon 6, nylon 66, and aromatic polyamide; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; fluororesins such as polytetrafluoroethylene, perfluoroethylene-propene copolymer, and ethylene-tetrafluoroethylene copolymer; liquid crystal polymers such as liquid crystal polyester and liquid crystal polyesteramide; and resins such as polyether ketone, polyether sulfone, polyarylene sulfide, and polyacrylonitrile. Two or more of these may be used. It is preferable to appropriately select and use from these organic fibers based on the tensile elongation at break and the combination with the thermoplastic resin (B) that is the matrix resin. In particular, it is preferable that the melting temperature of the organic fibers is 30°C to 150°C higher than the molding temperature (melting temperature) of the thermoplastic resin (B). Alternatively, organic fibers made from a resin that is incompatible with the thermoplastic resin (B) are preferred because they remain in a fibrous state within the molded article, thereby further improving the impact strength of the molded article. Examples of organic fibers with a high melting point include polyester fibers, liquid crystal polyester fibers, polyphenylene sulfide fibers, polyamide fibers, and PAN-based flame-resistant yarns that are said to not melt.

[0036] There are no particular limitations on the type of glass fiber used in the present invention, and known glass fibers 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] Generally, various binders are added to glass fibers to improve handling by suppressing the generation of fluff and static electricity during use and to improve adhesion to the thermoplastic resin (B) that serves as the matrix. Glass fibers to which these binders have been added can also be used in the present invention. The type of binder may be selected depending on the type of thermoplastic resin (B) that serves as the matrix. The amount of binder added to the glass fibers is preferably 0.1 to 3.0 mass% in terms of solid content, based on the total mass of the glass fibers after the binder has been added. When the amount of binder added is 0.1 mass% or more, the handleability and adhesiveness can be sufficiently improved. On the other hand, when the amount of binder added is 3.0 mass% or less, the impregnation of the thermoplastic resin (B) into the glass fibers can be more effectively promoted.

[0038] Examples of binders include coupling agents such as silane-based coupling agents (aminosilane, epoxysilane, acrylicsilane, etc.); polymers or modified products thereof (vinyl acetate resin, urethane resin, acrylic resin, polyester resin, polyether resin, phenoxy resin, polyamide resin, epoxy resin, polyolefin resin, etc.); and oligomers such as waxes (polyolefin wax, etc.). The above-mentioned polymers and oligomers are generally used in the form of aqueous dispersions obtained by dispersing in water with a surfactant, or aqueous solutions obtained by neutralizing or hydrating carboxyl groups or amide groups present in the polymer or oligomer skeleton. In addition to the above components, the binder may also contain antistatic agents (e.g., inorganic salts such as lithium chloride and potassium iodide, quaternary ammonium salts such as ammonium chloride and ammonium ethosulfate), lubricants (e.g., aliphatic ester, aliphatic ether, aromatic ester, or aromatic ether surfactants).

[0039] In the present invention, when glass fibers are contained in the composition, the content thereof is preferably 1 to 45 parts by weight per 100 parts by weight of the reinforcing fibers (A). If the content of glass fibers is less than 1 part by weight, the impact strength of the molded article decreases. The content of glass fibers 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, if the content of glass fibers exceeds 45 parts by weight, entanglement between fibers increases, the dispersibility of the glass fibers 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 glass fibers 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.

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

[0041] In the present invention, the thermoplastic resin (B) preferably has a molding temperature (melting temperature) of 200 to 450°C, and examples thereof include polyolefin resins, polystyrene resins, polyamide resins, halogenated vinyl resins, polyacetal resins, saturated polyester resins, polycarbonate resins, polyarylsulfone resins, polyarylketone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyaryletherketone resins, polyethersulfone resins, polyphenylene sulfide sulfone resins, polyarylate resins, and polyamide resins, all of which correspond to electrical insulators. Two or more of these may also be used.

[0042] Among the thermoplastic resins (B), polyolefin resins, polyamide resins, polycarbonate resins and polyarylene sulfide resins are more preferred because they are lightweight and have an excellent balance between mechanical properties and moldability.

[0043] The term "polyolefin resin" as used herein includes both unmodified and modified polyolefins. For example, an unmodified polypropylene resin is specifically a propylene homopolymer or a copolymer of propylene with at least one α-olefin, conjugated diene, non-conjugated diene, or the like. Examples of α-olefins include α-olefins having 2 to 12 carbon atoms (excluding propylene), such as 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. Examples of conjugated dienes and non-conjugated dienes include butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Two or more of these may be used. Examples of the skeletal structure of unmodified polypropylene resin include a propylene homopolymer, a random or block copolymer of propylene and the other monomers mentioned above, and a random or block copolymer of propylene and other thermoplastic monomers. Suitable examples include polypropylene, ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer. A propylene homopolymer is preferred from the viewpoint of further improving the rigidity of molded articles, and a random or block copolymer of propylene and the other monomers mentioned above is preferred from the viewpoint of further improving the impact strength of molded articles.

[0044] The modified polypropylene resin is preferably an acid-modified polypropylene resin, and more preferably a polypropylene resin having a carboxylic acid and / or a salt thereof bonded to the polymer chain. The acid-modified polypropylene resin can be obtained by various methods, for example, by graft polymerizing a polypropylene resin with a monomer having a neutralized or unneutralized carboxylic acid group and / or a monomer having a saponified or unsaponified carboxylic acid ester.

[0045] Here, examples of the monomer having a neutralized or unneutralized carboxylic acid group, or the monomer having a saponified or unsaponified carboxylic acid ester group include ethylenically unsaturated carboxylic acids, their anhydrides, and esters thereof, as well as compounds other than olefins having an unsaturated vinyl group.

[0046] Examples of ethylenically unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, and examples of their anhydrides include Nadic acid™ (endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, and citraconic anhydride.

[0047] Examples of esters of ethylenically unsaturated carboxylic acids include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and decyl (meth)acrylate. Acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, lauroyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, di Examples of the hydroxyl group-containing (meth)acrylic acid esters include ethylaminoethyl (meth)acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl acrylate, and examples of the hydroxyl group-containing (meth)acrylic acid esters include glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate, and examples of the aminoalkyl (meth)acrylates include 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, and N,N-dihydroxyethylaminoethyl (meth)acrylate.

[0048] Examples of the monomer having an unsaturated vinyl group other than olefins include isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and t-butylstyrene, amide group-containing vinyls such as acrylamide, methacrylamide, N-methylol methacrylamide, N-methylol acrylamide, diacetone acrylamide and maleic acid amide, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated sulfonic acids such as styrene sulfonic acid, sodium styrene sulfonate and 2-acrylamido-2-methylpropane sulfonic acid, and unsaturated phosphoric acids such as mono(2-methacryloyloxyethyl) acid phosphate and mono(2-acryloyloxyethyl) acid phosphate.

[0049] Two or more of these may be used. Among these, ethylenically unsaturated carboxylic acid anhydrides are preferred, with maleic anhydride being more preferred.

[0050] In order to improve the bending strength and tensile strength of the molded article, it is preferable to use both unmodified and modified polypropylene resins, and from the viewpoint of the balance between flame retardancy and mechanical properties in particular, it is preferable to use the unmodified and modified polypropylene resins in a weight ratio of 95 / 5 to 75 / 25, more preferably 95 / 5 to 80 / 20, and even more preferably 90 / 10 to 80 / 20.

[0051] Polyamide resins are resins whose main raw materials are amino acids, lactams, or diamines and dicarboxylic acids. Typical examples of the main raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, aliphatic diamines such as tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, and 5-methylnonamethylenediamine, aromatic diamines such as metaxylylenediamine and paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane. Alicyclic diamines such as hexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine; aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. Two or more of these may be used.

[0052] In the present invention, polyamide resins having a melting point of 200° C. or higher are particularly useful because of their excellent heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6 / 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene decamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polydodecamethylene dodecamide (nylon 1212), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 6T / 6), Examples of such a copolymer include polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene terephthalamide / poly(2-methylpentamethylene) terephthalamide copolymer (nylon 6T / M5T), polyxylylene adipamide (nylon XD6), polynonamethylene terephthalamide (nylon 9T), and copolymers thereof. Two or more of these may be used. Among these, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12 and nylon 9T are more preferred.

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

[0054] The polycarbonate resin is obtained by reacting a dihydric phenol with a carbonate precursor. It may also be a copolymer obtained using two or more dihydric phenols 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 per se, and the polycarbonate resins described in JP-A-2002-129027, for example, can be used.

[0055] Examples of dihydric phenols include 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)alkanes (such as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Two or more of these may be used. Among these, bisphenol A is preferred, as it allows the production of polycarbonate resins with superior impact resistance. On the other hand, copolymers obtained using bisphenol A and other dihydric phenols are excellent in terms of high heat resistance and low water absorption.

[0056] As the carbonate precursor, for example, a carbonyl halide, a carbonic acid diester, or a haloformate may be used, and specific examples thereof include phosgene, diphenyl carbonate, or a dihaloformate of a dihydric phenol.

[0057] In producing the polycarbonate resin from the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant for preventing oxidation of the dihydric phenol, and the like may be used as needed.

[0058] The polycarbonate resins of the present invention include branched polycarbonate resins copolymerized with trifunctional or higher polyfunctional aromatic compounds, polyester carbonate resins copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids, copolymer polycarbonate resins copolymerized with bifunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and bifunctional alcohols. These polycarbonate resins are also known. Two or more of these polycarbonate resins may be used.

[0059] The molecular weight of the polycarbonate resin is not specified, but one with a viscosity average molecular weight of 10,000 to 50,000 is preferred. A viscosity average molecular weight of 10,000 or higher can further improve the strength of molded articles. 15,000 or higher is more preferred, and 18,000 or higher is even more preferred. On the other hand, a viscosity average molecular weight of 50,000 or lower improves moldability. 40,000 or lower is more preferred, and 30,000 or lower is even more preferred. When two or more polycarbonate resins are used, it is preferable that the viscosity average molecular weight of at least one of them is within the above range. In this case, it is preferable to use a polycarbonate resin with a viscosity average molecular weight of more than 50,000, preferably more than 80,000, as the other polycarbonate resin. Such polycarbonate resins have high entropy elasticity, which is advantageous when used in conjunction with gas-assisted molding, etc., and also exhibit properties derived from high entropy elasticity (anti-drip properties, drawdown properties, and properties that improve melting properties such as improved jetting).

[0060] The viscosity average molecular weight (M) of the polycarbonate resin was calculated by inserting the specific viscosity (ηsp) measured at 20°C from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride into the following equation: ηsp / c = [η] + 0.45 × [η] ２ c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 －４ M ０．８３ c=0.7

[0061] In the present invention, examples of polyarylene sulfide resins include polyphenylene sulfide (PPS) resins, polyphenylene sulfone resins, polyphenylene sulfide ketone resins, and random or block copolymers thereof. Two or more of these may be used. Among these, polyphenylene sulfide resins are particularly preferred.

[0062] The polyarylene sulfide resin can be produced by any method, such as the method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or the method for obtaining a polymer having a relatively large molecular weight described in JP-B-52-12240 or JP-A-61-7332.

[0063] The obtained polyarylene sulfide resin may be subjected to various treatments such as crosslinking / polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution, or the like, or activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, or a functional group-containing disulfide compound.

[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 / sec. There is no particular lower limit, but it is preferably 5 Pa·s or more. Two or more polyarylene sulfide resins with different melt viscosities may be used in combination. The melt viscosity can be measured using a Capilograph (manufactured by Toyo Seiki Co., Ltd.) device under conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

[0065] As the polyarylene sulfide resin, polyphenylene sulfide resins commercially available as "TORELINA" (registered trademark) manufactured by Toray Industries, Inc., "DIC.PPS" (registered trademark) manufactured by DIC Corporation, "DURAFIDE" (registered trademark) manufactured by Polyplastics Co., Ltd., etc. can also be used.

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

[0067] It is preferable that the thermoplastic resin (B) contains (Ba) and (Bb) because this increases the tensile strength and impact strength of the molded article. There are no particular restrictions on the types of thermoplastic resins (Ba) and (Bb) contained in the thermoplastic resin (B). However, it is preferable to use the type of thermoplastic resin described below as a thermoplastic resin with excellent mechanical strength as the thermoplastic resin (Ba), and it is preferable to use the type of thermoplastic resin described below as a thermoplastic resin with particularly excellent impact strength as the thermoplastic resin (Bb). Depending on the desired effect, it is also preferable to use two or more of these thermoplastic resins in combination. In this case, the combination of thermoplastic resins is appropriately selected depending on the desired properties.

[0068] Furthermore, the thermoplastic resin (B) in the composition of the present invention may be a melt-kneaded resin composition (B1), which is composed of a thermoplastic resin (Ba), a resin (Bb) having a reactive functional group, and a compound (Bc) produced by the reaction of (Ba) with (Bb), and contains 20 to 94.5 parts by weight of the melt-kneaded resin composition (B1) obtained by melt-kneading the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group, per 100 parts by weight in total of the reinforcing fibers (A), the melt-kneaded resin composition (B1), and the rosin resin (C).

[0069] <Thermoplastic Resin (Ba)> In the present invention, the thermoplastic resin (Ba) preferably has a molding temperature (melting temperature) of 200 to 450°C, and examples thereof include polyolefin resins, polystyrene resins, polyamide resins, halogenated vinyl resins, polyacetal resins, saturated polyester resins, polycarbonate resins, polyarylsulfone resins, polyarylketone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyaryletherketone resins, polyethersulfone resins, polyphenylene sulfide sulfone resins, polyarylate resins, and polyamide resins, all of which are electrical insulators. Two or more of these may also be used. Among these, polyolefin resins, polyamide resins, polycarbonate resins, and polyphenylene sulfide resins are preferred from the viewpoints of moldability, mechanical properties, and light weight.

[0070] <Resin (Bb) Having a Reactive Functional Group> The base resin for the resin (Bb) having a reactive functional group is not particularly limited, and may be at least one resin selected from, for example, polyamide, polyester, polyphenylene sulfide, polyphenylene oxide, polycarbonate, polylactic acid, polyacetal, polysulfone, tetrafluoroethylene, polyetherimide, polyamideimide, polyimide, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, polyethylene, polypropylene, styrene-based resins such as polystyrene and ABS, rubber polymers, polyalkylene oxides, etc., and is different from the polyamide resin (Ba). Among these, as the base resin for the resin (Bb), from the viewpoint of ease of introduction of reactive functional groups, resins selected from polyolefin resins such as polyethylene resins and polypropylene resins, styrene-based resins, and rubber polymers are more preferred, and from the viewpoint of imparting impact absorption, rubber polymers are even more preferred.

[0071] The rubbery polymer is a polymer containing a polymer with a low glass transition temperature, in which some of the intermolecular bonds are constrained by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc. The glass transition temperature of the rubbery polymer is preferably 25° C. or lower. A glass transition temperature exceeding 25° C. is undesirable because it results in poor impact resistance.

[0072] Examples of rubbery polymers include diene rubbers such as polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of these block copolymers, acrylonitrile-butadiene copolymers, and butadiene-isoprene copolymers; random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins; ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers; ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-acrylic acid esters and ethylene-methacrylic acid esters; copolymers in which a part of the unsaturated carboxylic acid is gold; Preferred examples of the polymerizable monomer include metal salts such as ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymers, such as ethylene-acrylic acid-metal acrylic acid salt and ethylene-methacrylic acid-metal methacrylic acid salt; acrylic acid ester-butadiene copolymers, acrylic elastic polymers, such as butyl acrylate-butadiene copolymer; copolymers of ethylene and fatty acid vinyl, such as ethylene-vinyl acetate; ethylene-propylene-ethylidenenorbornene copolymer, ethylene-propylene-hexadiene copolymer and other ethylene-propylene non-conjugated diene terpolymers; butylene-isoprene copolymer; chlorinated polyethylene; and thermoplastic elastomers, such as polyamide elastomers and polyester elastomers.

[0073] When used for the thermoplastic resin (Ba), from the viewpoint of obtaining excellent impact strength, an ethylene-unsaturated carboxylic acid ester copolymer, an ethylene-propylene random copolymer or block copolymer, an ethylene-butene random copolymer or block copolymer, or a copolymer of ethylene and an α-olefin is preferably used.

[0074] The unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is preferably a (meth)acrylic acid ester. Specific examples of unsaturated carboxylic acid esters include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate. Here, "(meth)acrylic acid" means "acrylic acid or methacrylic acid." The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the copolymer is not particularly limited, but is preferably in the range of 90 / 10 to 10 / 90, more preferably 85 / 15 to 15 / 85. The number-average molecular weight of the ethylene-unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably in the range of 1,000 to 70,000 from the viewpoints of fluidity and mechanical properties.

[0075] The reactive functional group contained in the resin (Bb) having a reactive functional group is not particularly limited as long as it reacts with the functional group present in the thermoplastic resin (Ba), but preferably includes at least one selected from an amino group, a carboxyl group, a metal salt of a carboxyl group, a hydroxyl group, an epoxy group, an acid anhydride group, an isocyanate group, a mercapto group, an oxazoline group, a sulfonic acid group, etc. Among these, groups selected from an amino group, a carboxyl group, a metal salt of a carboxyl group, an epoxy group, an acid anhydride group, and an oxazoline group are more preferably used because they have high reactivity and are less susceptible to side reactions such as decomposition and crosslinking.

[0076] When an acid anhydride group is introduced into a rubbery polymer, the method can be carried out by a known technique and is not particularly limited. For example, a method of copolymerizing an acid anhydride such as maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, or 1-butene-3,4-dicarboxylic anhydride with a monomer that is a raw material for the rubbery polymer, or a method of grafting an acid anhydride onto a rubbery polymer can be used.

[0077] Furthermore, when an epoxy group is introduced into a rubbery polymer, the method can be carried out by a known technique and is not particularly limited. For example, a method of copolymerizing a vinyl monomer having an epoxy group, such as a glycidyl ester compound of an α,β-unsaturated acid such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, or glycidyl itaconate, with a monomer that is a raw material for the rubbery polymer, a method of polymerizing a rubbery polymer using a polymerization initiator or chain transfer agent having an epoxy group, or a method of grafting an epoxy compound onto a rubbery polymer can be used.

[0078] Furthermore, when an oxazoline group is introduced into a rubbery polymer, the method can be carried out by a known technique and is not particularly limited. For example, a method can be used in which a vinyl monomer having an oxazoline group, such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acroyl-oxazoline, or 2-styryl-oxazoline, is copolymerized with a monomer that is a raw material for the rubbery polymer.

[0079] The number of functional groups per molecular chain in the resin (Bb) having a reactive functional group is not particularly limited, but is usually preferably 1 to 10, and more preferably 1 to 5 in order to reduce side reactions such as crosslinking.

[0080] The melt-kneaded resin composition (B1) of the present invention comprises a thermoplastic resin (Ba), a resin (Bb) having a reactive functional group, and a compound (Bc) produced by the reaction of (Ba) with (Bb). The melt-kneaded resin composition (B1) can be obtained by melt-kneading the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group. Furthermore, since the resin (Bb) has a reactive functional group, (Bc) is produced by the reaction of (Ba) with (Bb) during melt-kneading of the resins (Ba) and (Bb). The melt-kneaded resin composition (B1) is obtained as 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 particulate form as a dispersed phase. The structure of the particles made of the resin (Bb) is highly controlled, which greatly contributes to improving impact resistance. The number average particle diameter of the particles of resin (Bb) contained in the melt-kneaded resin composition (B1), which is a thermoplastic resin composition in which thermoplastic resin (Ba) and resin (Bb) are mixed to form a matrix resin and resin (Bb) is dispersed in the matrix resin in particulate form, must be 10 to 1,000 nm. If the number average particle diameter of the particles is less than 10 nm, the impact resistance characteristic of the present invention is not exhibited, and 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 amount of particles of resin (Bb) with a highly controlled structure, a fiber-reinforced thermoplastic resin composition molded product with an excellent balance between rigidity and impact resistance can be obtained.

[0081] Furthermore, the fiber-reinforced thermoplastic resin composition molded article of the present invention preferably contains fine particles of compound (Bc) having an average particle diameter of 1 to 100 nm produced by the reaction of thermoplastic resin (Ba) and resin (Bb) in particles made of resin (Bb). Furthermore, it is preferable that the area ratio of compound (Bc) produced by the reaction of components (Ba) and (Bb) in the particles made of resin (Bb) is 20% or more. Even if the amount of resin (Bb) forming the dispersed phase is small, by controlling the structure within the dispersed phase as described above, a fiber-reinforced thermoplastic resin composition molded article having an excellent balance of rigidity and impact resistance can be obtained.

[0082] Note that known techniques can be applied to the morphology observation method. For example, the cross-sectional center of the test specimen is cut into 1-2 mm squares, and the resin (B2) having a reactive functional group is stained with ruthenium tetroxide. Ultrathin sections of 0.1 μm or less (approximately 80 nm) in thickness are then obtained using an ultramicrotome, and the resin portion of the section (excluding the reinforcing fibers) consisting of the thermoplastic resin (Ba), resin (Bb), and compound (Bc) is observed using a transmission electron microscope. The number average particle size (Xn) of the particles is determined by randomly extracting 400 or more particles from the obtained image, analyzing the particle size distribution using Scion Corporation's image analysis software "Scion Image," and using the following formula: Number average particle size (Xn) = Σ(Xi × n) / Σn, where Xi is the particle size, n is the number of particles corresponding to the particle size (Xi) (i = 1, 2, 3, ..., n).

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

[0084] The area ratio of compound (Bc) in particles made of resin (Bb) is determined by analyzing the area of ​​resin (Bb) and the area of ​​compound (Bc) from an image magnified 35,000 times using a transmission electron microscope and using image analysis software "Scion Image" manufactured by Scion Corporation, and then using the following formula: Sn = Sp / (Sa2 + Sp) Sn: area ratio (Sn) occupied by compound (Bc) in particles made of resin (Bb) Sa2: area occupied by resin (Bb) Sp: area occupied by compound (Bc).

[0085] In the present invention, the method for producing the melt-kneaded resin composition (B1) is not particularly limited, but the following method, for example, is effective.

[0086] One method for producing the melt-kneaded resin composition (B1) is to feed a thermoplastic resin (Ba) and a resin (Bb) having a reactive functional group into a twin-screw extruder having a ratio L / D0 of the screw length L to the screw diameter D0 of 50 or more and having a plurality of full-flight zones and kneading zones, and melt-kneading the resin under conditions that satisfy Pkmax ≧ Pfmin + 0.3, where Pkmax (MPa) is the maximum resin pressure among the resin pressures in the kneading zones in the screw, and Pfmin (MPa) is the minimum resin pressure among the resin pressures in the full-flight zones in the screw.

[0087] From the viewpoint of improving kneading properties and reactivity, the L / D0 value is more preferably 60 to 200, and even more preferably in the range of 80 to 200. Furthermore, when using a twin-screw extruder with an L / D0 of less than 50, it is preferable to perform kneading multiple times to achieve a calculated L / D0 value of 50 or more through which the resin composition passes. L / D0 is the value obtained 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 segment located at the position (feed port) where the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group are supplied at the base of the screw to the tip of the screw. The screws of twin-screw extruders are configured by combining screw segments with different lengths and shape characteristics, such as full-flight and kneading disks. In addition, in an extruder, the side where raw materials are supplied is sometimes referred to as the upstream side, and the side where the molten resin is discharged is sometimes referred to as the downstream side.

[0088] When the melt-kneaded resin composition (B1) is produced using a twin-screw extruder having an L / D0 of 50 or more, the screw of the twin-screw extruder preferably has a plurality of full-flight zones and kneading zones, from the viewpoint of improving kneading properties and reactivity. The full-flight zone is composed of one or more full flights, and the kneading zone is composed of one or more kneading disks.

[0089] Of the resin pressures indicated by resin pressure gauges installed at multiple locations in the kneading zone, the maximum resin pressure in the kneading zone is defined as Pkmax (MPa), and of the resin pressures indicated by resin pressure gauges installed at multiple locations in the full flight zone, the minimum resin pressure in the full flight zone is defined as Pfmin (MPa). It is preferable to manufacture under conditions where the Pkmax value is (Pfmin + 0.3) or greater, and it is even more preferable to manufacture under conditions where the Pkmax value is (Pfmin + 0.5) or greater.

[0090] A kneading zone consisting of one or more kneading discs has better kneading and reactivity of molten resin than a full-flight zone consisting of one or more full-flight discs. Filling the kneading zone with molten resin dramatically improves kneading and reactivity. The resin pressure is one indicator of the state of molten resin filling, and the higher the resin pressure, the more molten resin is filled. In other words, when using a twin-screw extruder, the reaction can be effectively promoted by increasing the resin pressure in the kneading zone to a certain extent compared to the resin pressure in the full-flight zone.

[0091] There are no particular limitations on the method for increasing the resin pressure in the kneading zone, but methods such as introducing a reverse screw zone that has the effect of pushing the molten resin back upstream or a seal ring zone that has the effect of accumulating the molten resin between kneading zones or downstream of the kneading zones are preferably used. The reverse screw zone or seal ring zone consists of one or more reverse screws or one or more seal rings, and these can also be combined.

[0092] For example, when a reverse screw zone is introduced between kneading zones or downstream of a kneading zone, it is preferable from the viewpoint of kneading property and reactivity that the reverse screw zone have a length Lr / D0 = 0.1 to 10, where Lr is the length of the reverse screw zone. 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 all of the reverse screw zones satisfy the above Lr / D0 range. The length Lr of the reverse screw zone is defined as the distance between a perpendicular line from the upstream end of the most upstream reverse screw constituting the reverse screw zone to the center line of the screw shaft and a perpendicular line from the downstream end of the most downstream reverse screw constituting the reverse screw zone to the center line of the screw shaft.

[0093] When the melt-kneaded resin composition (B1) is produced using a twin-screw extruder having an L / D0 of 50 or more, the extrusion rate is preferably 0.01 kg / h or more, more preferably 0.05 kg / h to 1 kg / h, even more preferably 0.08 to 0.5 kg / h, and most preferably 0.1 to 0.3 kg / h per screw rpm. Here, the extrusion rate refers to the weight (kg) of the melt-kneaded product discharged from the extruder per hour.

[0094] The preferable range of values ​​relating to the extrusion rate in the twin-screw extruder is based on the extrusion rate of a twin-screw extruder with a screw diameter of 41 mm. When the screw diameter is significantly different, for example, when a twin-screw extruder with a diameter of less than 30 mm or more than 50 mm is used, the extrusion rate can be interpreted as decreasing or increasing, preferably according to the 2.5th power law or the 3rd power law, more preferably according to the 2.5th power law, with respect to the screw diameter ratio before and after scale-down or scale-up.

[0095] For example, when a twin-screw extruder having a screw diameter of 20 mm is used, assuming that the extrusion rate follows the 2.5 power law of the screw diameter ratio before and after scale-down, the extrusion rate of the melt-kneaded product per rpm of screw rotation speed is preferably 0.0017 kg / h or more, more preferably 0.0083 to 0.17 kg / h, even more preferably 0.013 to 0.083 kg / h, and most preferably 0.017 to 0.050 kg / h.

[0096] Furthermore, when a twin-screw extruder having a screw diameter of 100 mm is used, assuming that the extrusion rate follows the 2.5th power law of the screw diameter ratio before and after scale-up, the extrusion rate of the melt-kneaded product per 1 rpm of the screw is preferably 0.093 kg / h or more, more preferably 0.46 to 9.29 kg / h, even more preferably 0.74 to 4.65 kg / h, and most preferably 0.93 to 2.79 kg / h.

[0097] The rotation speed of the screw is not particularly limited, but 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, and more preferably 1.5 to 25 minutes. This residence time is a value representing the average residence time from when the raw materials are supplied to the twin-screw extruder until they are discharged. The residence time is measured in a steady melt-kneaded state in which an uncolored melt-kneaded product is adjusted to a predetermined extrusion rate, and is measured from the time when about 1 g of a colorant is added together with the raw materials from the base of the screw where the raw materials are supplied, until the extrusion from the extruder outlet reaches the time when the degree of coloration of the extrudate by the colorant is maximized.

[0099] When the melt-kneaded resin composition (B1) is produced using a twin-screw extruder having an L / D0 of 50 or more, the screws of the twin-screw extruder are not particularly limited, and screws of a fully intermeshing type, a partially intermeshing type, a non-intermeshing type, etc. can be used. From the viewpoint of kneading property and reactivity, a fully intermeshing type screw is preferred. Furthermore, the rotation direction of the screw may be either the same direction or counter-direction, but from the viewpoint of kneading property and reactivity, a same-direction rotation is preferred. As the screw, a fully intermeshing type rotating in the same direction is most preferred.

[0100] The screw configuration of the twin-screw extruder is preferably a combination of full flight and / or kneading discs, but a screw configuration that effectively applies a shear field to the molten resin composition is preferred. Therefore, as described above, it is preferable that the screw of the twin-screw extruder has multiple kneading zones in the longitudinal direction, each of which is composed of one or more kneading discs. The total length of these kneading zones is preferably 5 to 50%, more preferably 10 to 40%, and even more preferably 15 to 30% of the total length of the screw.

[0101] If the length of each kneading zone in the screw of a twin-screw extruder is Lk, it is preferable from the viewpoint of kneading ability and reactivity that 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. The length Lk of a kneading zone is the distance between a perpendicular line from the upstream end of the most upstream kneading disc constituting the kneading zone to the center line of the screw shaft and a perpendicular line from the downstream end of the most downstream kneading disc constituting the kneading zone to the center line of the screw shaft. Furthermore, it is preferable that the kneading zones of a twin-screw extruder are arranged throughout the entire area without being unevenly distributed at a specific position within the screw.

[0102] In order to remove reaction by-products or thermal degradation products, a vent vacuum zone is preferably provided and melt-kneaded at a reduced pressure of −0.07 MPa or less, more preferably −0.08 MPa or less. Here, the term “gauge pressure” refers to the pressure when atmospheric pressure is zero. The lower the pressure, the higher the degree of vacuum and the greater the ability to remove volatile components. A vent vacuum zone with a gauge pressure of more than −0.07 MPa, i.e., a low degree of vacuum, is undesirable because it is not possible to sufficiently remove the volatile components, leaving impurities in the polyamide resin composition (B). By sufficiently removing the volatile components in the vent vacuum zone, it is possible to reduce the amount of impurities in the melt-kneaded product. There are no particular limitations on the number of vent vacuum zones, and it is preferable to install one or more. There are also no particular limitations on the location of the vent vacuum zone, but installing at least one at a position L / D0 = 0 to 10 before the sampling position is preferred, as this enables effective removal of the volatile components.

[0103] The maximum resin temperature is preferably controlled to 180°C to 330°C during melt kneading, and more preferably 200°C to 325°C. The maximum resin temperature here refers to the highest temperature measured using resin thermometers evenly installed at multiple positions in the extruder. If the maximum resin temperature is less than 180°C, the reactivity between polymers is low, and if it exceeds 330°C, thermal decomposition of the polymer progresses.

[0104] When a twin-screw extruder is used, it is preferable to melt-knead the materials by introducing an inert gas into the material inlet port in order to suppress thermal degradation. As the inert gas, nitrogen gas is preferable.

[0105] The second method for producing the melt-kneaded resin composition (B1) is a method in which the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group are melt-kneaded under extensional flow. Extensional flow kneading has a higher dispersion efficiency than the shear flow generally used in melt-kneading, and therefore the reaction proceeds efficiently, especially in the case of alloying accompanied by a reaction such as reactive processing.

[0106] When producing the melt-kneaded resin composition (B1) by melt-kneading under extensional flow, melt-kneading using an extruder is preferably used, and examples of the extruder include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder having three or more screws. Among these, a single-screw extruder and a twin-screw extruder are preferably used, and a twin-screw extruder is particularly preferably used. The screws of such twin-screw extruders are not particularly limited, and screws of a fully intermeshing type, an incompletely intermeshing type, a non-intermeshing type, etc. can be used. From the viewpoint of kneading property and reactivity, a fully intermeshing type is preferred. Furthermore, the rotation direction of the screws may be either unidirectional or counterdirectional, but from the viewpoint of kneading property and reactivity, a unidirectional rotation is preferred. The most preferred screws are unidirectionally rotating fully intermeshing types.

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

[0108] If the length of the extensional flow zone in the screw of the extruder is Lk and the screw diameter is D0, then from the viewpoint of kneading ability and reactivity, Lk / D0 is preferably 0.2 to 10, more preferably 0.3 to 9, and even more preferably 0.5 to 8. When multiple extensional flow zones are provided, it is preferable that all of the respective extensional flow zones satisfy the above Lk / D0 range. Furthermore, in the present invention, it is preferable that the extensional flow zones are disposed throughout the entire screw, without being concentrated at a specific position within the screw.

[0109] Preferred examples of the screw configuration of the extensional flow zone include a twist kneading disk consisting of a kneading disk, in which the helical angle θ, which is the angle between the apex on the disk tip side and the apex on the rear side of the kneading disk, is in the range of 0°<θ<90° in the half-rotation direction of the screw; a flight screw, in which the flight portion of the flight screw is formed with a resin passage whose cross-sectional area decreases from the screw tip side to the rear end side; and a resin passage in the extruder in which the cross-sectional area through which the molten resin passes gradually decreases.

[0110] The extrusion rate per 1 rpm of the screw is preferably 0.01 kg / h or more. The extrusion rate refers to the weight (kg) of the molten mixture extruded per hour from the extruder. If the extrusion rate per 1 rpm of the screw is less than 0.01 kg / h, the extrusion rate relative to the rotation speed is insufficient, the residence time in the extruder becomes too long, causing thermal degradation, and the filling rate of the resin in the extruder becomes very low, resulting in the problem of insufficient kneading. The rotation speed of the screw is not particularly limited, but is preferably 10 rpm or more, more preferably 50 rpm or more, and even more preferably 80 rpm or more. 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 residence time in the extruder is preferably 1 to 30 minutes, more preferably 1.5 to 28 minutes, and even more preferably 2 to 25 minutes. The residence time is a value representing the average residence time from when raw materials are fed into the extruder until they are discharged. The residence time is measured in a steady melt-kneaded state where an uncolored resin composition is adjusted to a predetermined extrusion rate. The residence time is measured from the time when approximately 1 g of colorant is added together with the raw materials from the base of the screw where the raw materials are fed, until the extrusion from the extruder outlet reaches the point where the coloring degree of the colorant in the extrudate reaches its maximum. A residence time of less than 1 minute is undesirable because the reaction time in the extruder is too short and the reaction is not sufficiently promoted. A residence time of more than 30 minutes is undesirable because the long residence time causes thermal degradation of the resin.

[0112] In both cases where the melt-kneaded resin composition (B1) is produced using a twin-screw extruder having an L / D0 of 50 or more, and where the melt-kneaded resin composition (B1) is produced by melt-kneading while undergoing extensional flow, it is preferable that the blending ratio of the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group is 80 to 60% by weight for the thermoplastic resin (Ba) and 20 to 40% by weight for the resin (Bb), because this allows the thermoplastic resin (Ba) to form a continuous phase and the resin (Bb) to form a dispersed phase, and particles made of the resin (Bb) contain compounds (Bc) of 1 to 100 nm produced by the reaction of (Ba) and (Bb), and further the area ratio occupied by the compound (Bc) is likely to be 20% or more.

[0113] The composition of the present invention contains, in addition to the reinforcing fibers (A) and the thermoplastic resin (B), a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more. The rosin resin (C) is not particularly limited, and various known rosin resins can be used. Examples of the rosin resin include purified rosin obtained by purifying natural rosin (gum rosin, tall oil rosin, wood rosin) derived from Masson pine, Slash pine, Merkus pine, Siberian pine, Loblolly pine, and Great King pine by vacuum distillation, steam distillation, extraction, recrystallization, etc. (hereinafter, natural rosin and purified rosin are collectively referred to as unmodified rosin); hydrogenated rosin obtained by hydrogenating the unmodified rosin; disproportionated rosin obtained by disproportionating the unmodified rosin; polymerized rosin obtained by polymerizing the unmodified rosin; acid-modified rosins such as acrylated rosin, maleated rosin, and fumarated rosin; esters of the rosins (hereinafter, these esters are referred to as rosin esters); rosin phenolic resin; and rosin polyol. The rosin resins may 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 mgKOH / g or more is at least one selected from the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin ester, and rosin polyol.

[0115] By making the acid value and / or hydroxyl value of the rosin resin (C) resin having an acid value and / or hydroxyl value of 100 mgKOH / g or more, the dispersibility of fibers in the fiber-reinforced resin can be further improved, resulting in excellent mechanical strength and improved appearance quality, particularly blackness, of the molded article. 120 mgKOH / g is more preferable, 130 mgKOH / g is even more preferable, and 150 mgKOH / g or more is most preferable.

[0116] The acid value and / or hydroxyl value of the rosin resin is preferably 300 mgKOH / g or less. By setting the acid value and / or hydroxyl value to 300 mgKOH / g or less, it is possible to suppress the modification of the thermoplastic resin (B) that is the matrix resin, and to suppress the decrease in tensile strength and impact strength. It is preferably 270 mgKOH / g or less, more preferably 260 mgKOH / g or less, and even more preferably 250 mgKOH / g or less.

[0117] In the present invention, the hydroxyl value and acid value are values ​​measured in accordance with JIS K 0070.

[0118] The rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is preferably at least one selected from the group consisting of hydrogenated rosin, polymerized rosin, acid-modified rosin, rosin ester, and rosin polyol, and particularly preferably at least one selected from the group consisting of acid-modified rosin or rosin polyol, in view of excellent mechanical strength in a fiber-reinforced resin.

[0119] Acid-modified rosin, unmodified rosin ester, hydrogenated rosin ester, disproportionated rosin ester, polymerized rosin ester, α,β-unsaturated carboxylic acid-modified rosin ester, rosin phenolic resin, and rosin polyol will be described below.

[0120] (Acid-Modified Rosin) Acid-modified rosin can be obtained by subjecting the unmodified rosin or disproportionated rosin to an addition reaction with an α,β-unsaturated carboxylic acid. The α,β-unsaturated carboxylic acid is not particularly limited, and various known α,β-unsaturated carboxylic acids can be used. Specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and muconic anhydride. Among these, acrylic acid, maleic acid, maleic anhydride, and fumaric acid are preferred. The amount of α,β-unsaturated carboxylic acid used is typically about 1 to 20 parts by weight, preferably about 1 to 3 parts by weight, per 100 parts by weight of the unmodified rosin, due to its excellent emulsifying properties. The α,β-unsaturated carboxylic acid may be used alone or in combination of two or more. The method for producing the α,β-unsaturated carboxylic acid-modified rosin is not particularly limited, but may include, for example, adding the α,β-unsaturated carboxylic acid to the unmodified rosin or disproportionated rosin melted under heating, and reacting for about 1 to 9 hours at a temperature of about 180° C. to 240° C. The reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system.

[0121] Furthermore, in the above reaction, known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, and Bronsted acids such as paratoluenesulfonic acid and methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01% by mass to 10% by mass relative to the unmodified rosin. Furthermore, the α,β-unsaturated carboxylic acid-modified rosin may be an α,β-unsaturated carboxylic acid-modified rosin that has been further subjected to hydrogenation, as described below. The α,β-unsaturated carboxylic acid-modified rosin may contain a resin acid derived from the unmodified rosin or disproportionated rosin.

[0122] (Unmodified Rosin Ester) Unmodified rosin ester can be obtained by reacting the unmodified rosin with an alcohol. The reaction between the unmodified rosin and the alcohol can be carried out in the presence or absence of a solvent, optionally with an esterification catalyst, at approximately 250°C to 280°C for approximately 1 to 8 hours. The alcohol is 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 dimer diol; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol and diglycerin; and hexahydric alcohols such as dipentaerythritol. Among these, polyhydric alcohols having two or more hydroxyl groups are preferred, with glycerin and pentaerythritol being particularly preferred. The above alcohols may be used alone or in combination of two or more.

[0123] (Hydrogenated Rosin Ester) The hydrogenated rosin ester is obtained by further reacting the hydrogenated rosin obtained by hydrogenating the unmodified rosin with an alcohol for esterification. The hydrogenated rosin can be obtained by various known means. Specifically, for example, the unmodified rosin may be heated and reacted (hydrogenated) under hydrogen pressure in the presence of a hydrogenation catalyst. Various known hydrogenation catalysts can be used, such as supported catalysts and metal powders. Supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon, and metal powders include nickel and platinum. The amount of the catalyst used is typically about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the rosin used as a raw material. The hydrogen pressure used when hydrogenating the unmodified rosin is about 2 to 20 MPa, preferably about 5 to 20 MPa. The reaction temperature when the unmodified rosin is hydrogenated is about 100 to 300°C, preferably about 150 to 300°C.

[0124] The hydrogenation may be carried out, if necessary, with the unmodified rosin dissolved in a solvent. The solvent used is not particularly limited, as long as it is inert to the reaction and readily dissolves the raw materials and products. Specifically, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. can be used alone or in combination with two or more. The amount of solvent used is not particularly limited, but typically, the solvent is used so that the solids content relative to the unmodified rosin is 10% by mass or more, preferably in the range of approximately 10% to 70% by mass. The reaction conditions for the hydrogenated rosin and alcohols may be such that the hydrogenated 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 hour to 8 hours. The alcohols used in esterifying the hydrogenated rosin are the same as those described above. The order of the hydrogenation reaction and the esterification reaction is not limited to the above, and the hydrogenation reaction may be carried out after the esterification reaction. The resulting hydrogenated rosin ester may be further subjected to the above-mentioned hydrogenation reaction.

[0125] (Disproportionated Rosin Ester) The disproportionated rosin ester is obtained by further reacting the disproportionated rosin obtained by disproportionating the unmodified rosin with an alcohol for esterification. The disproportionated rosin can be obtained by various known means. Specifically, for example, the unmodified rosin may be heated in the presence of a disproportionation catalyst to cause a reaction (disproportionation). Examples of the disproportionation catalyst include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; iodine; and iodides such as iron iodide. The amount of the catalyst used is typically about 0.01 to 5 parts by mass, preferably about 0.01 to 1 part by mass, per 100 parts by mass of the raw rosin. The reaction temperature during disproportionation of the unmodified rosin is about 100 to 300°C, preferably about 150 to 290°C. The reaction conditions for the disproportionated rosin and alcohols may be such that the disproportionated rosin and alcohols are reacted in the presence or absence of a solvent, with an esterification catalyst added as necessary, at about 250°C to 280°C for about 1 hour to 8 hours. The alcohols used in esterifying the disproportionated rosin are the same as those described above. The order of the disproportionation reaction and the esterification reaction is not limited to the above, and the disproportionation reaction may be carried out after the esterification reaction.

[0126] (Polymerized Rosin Ester) Polymerized rosin ester can be obtained by reacting polymerized rosin with alcohols. Polymerized rosin is a rosin derivative containing dimerized resin acid. Known methods can be used to produce the polymerized rosin. Specifically, for example, the unmodified rosin is reacted in a solvent such as toluene or xylene containing a catalyst 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 hour to 5 hours. Specific examples of the polymerized rosin include gum-based polymerized rosin using gum rosin as a raw material (e.g., "Polymerized Rosin B-140," manufactured by Shinzhou (Wuping) Hayashi Chemical Co., Ltd.), tall oil-based polymerized rosin using tall oil rosin (e.g., "Silvatack 140," manufactured by Arizona Chemical Co.), and wood-based polymerized rosin using wood rosin (e.g., "Dimalex," manufactured by Hercules). The polymerized rosin may be prepared by subjecting the polymerized rosin to various treatments, such as hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification, such as acrylate, maleinization, and fumaration. These treatments may be performed alone or in combination. The reaction between the polymerized rosin and alcohols may be carried out 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 hour to 8 hours. The polymerized rosin may also be reacted with the unmodified rosin in combination with the alcohol. The alcohols used in esterifying the polymerized rosin are the same as those described above. The order of the polymerization reaction and the esterification reaction is not limited to the above; the polymerization reaction may be carried out after the esterification reaction.

[0127] (α,β-Unsaturated Carboxylic Acid Modified Rosin Ester) The α,β-unsaturated carboxylic acid modified rosin ester can be obtained by reacting the above-mentioned α,β-unsaturated carboxylic acid modified rosin with an alcohol. The conditions for the reaction between the above-mentioned α,β-unsaturated carboxylic acid modified rosin and the alcohol are not particularly limited. For example, the alcohol can be added to the α,β-unsaturated carboxylic acid modified rosin melted under heating, and the reaction can be carried out at a temperature of about 250°C to 280°C for about 15 to 20 hours. The reaction can also be carried out while blowing an inert gas such as nitrogen into a sealed reaction system, and the aforementioned catalyst can also be used. The alcohol used in esterifying the α,β-unsaturated carboxylic acid modified rosin is the same as described above.

[0128] (Rosin Phenolic Resin) Rosin phenolic resin is obtained by reacting the unmodified rosin with a phenol. The phenol is not particularly limited, and various known phenols can be used. Specific examples include alkylphenols such as cresol, butylphenol, octylphenol, and nonylphenol, phenol, bisphenols, and naphthols. These phenols may be used alone or in combination. The amount of phenol used is typically about 0.8 to 1.5 moles per mole of the raw rosin. The method for producing the rosin phenolic resin is not particularly limited, but examples include a method in which the unmodified rosin and phenols are heated and reacted, if necessary, in the presence of an acid catalyst. The reaction temperature is typically 180 to 350°C, and the reaction time is about 6 to 18 hours. The acid catalyst that can be used in this reaction is not particularly limited, but examples include inorganic acid catalysts such as sulfuric acid, hydrogen chloride, and boron trifluoride, and organic acid catalysts such as paratoluenesulfonic acid and methanesulfonic acid. When an acid catalyst is used, it is sufficient to use about 0.01 to 1.0 part by mass per 100 parts by mass of the unmodified rosin. The rosin phenolic resin may also be an ester obtained by further reacting the resin obtained by the above reaction with an alcohol. The alcohol used in this case is the same as above.

[0129] (Rosin Polyol) Rosin polyol is a compound having at least two rosin skeletons and at least two hydroxyl groups in the molecule. Examples of the rosin polyol include a reaction product of the unmodified rosin, hydrogenated rosin, or disproportionated rosin with an epoxy resin (see JP-A-5-155972). Examples of the epoxy resin include bisphenol-type epoxy resins, novolac-type epoxy resins, resorcinol-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, aliphatic polyepoxy compounds, alicyclic epoxy compounds, glycidylamine-type epoxy compounds, glycidyl ester-type epoxy compounds, monoepoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy group-containing polyester resins, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins, stilbene-type epoxy compounds, triazine-type epoxy compounds, fluorene-type epoxy compounds, triphenolmethane-type epoxy compounds, alkyl-modified triphenolmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, and aryl alkylene-type epoxy compounds.

[0130] Examples of the bisphenol type epoxy resin 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, and tetrabromobisphenol A type epoxy resin.

[0131] Examples of the novolac epoxy resin include cresol novolac epoxy resin, phenol novolac epoxy resin, α-naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, and brominated phenol novolac epoxy resin.

[0132] Examples of the aliphatic polyepoxy compound 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 alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), and lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0134] Examples of the glycidylamine type epoxy compound include tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, triglycidyl meta-aminophenol, and tetraglycidyl meta-xylylenediamine.

[0135] Examples of the glycidyl ester type epoxy compound include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.

[0136] The method for producing the rosin polyol is not particularly limited, but examples include a method in which the unmodified rosin, hydrogenated rosin, or disproportionated rosin is subjected to a ring-opening addition reaction with an epoxy resin in the presence of a catalyst at 120° C. to 200° C. Examples of the catalyst that can be used include amine catalysts such as trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, and 2-methylimidazole; quaternary ammonium salts such as benzyltrimethylammonium chloride; Lewis acids; boric acid esters; organometallic compounds; and organometallic salts.

[0137] The softening point of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is 80°C to 200°C, and is preferably about 80°C to 180°C, and more preferably about 90°C to 160°C, from the viewpoints of excellent mechanical strength in a fiber-reinforced resin and excellent handleability and processability.

[0138] The number-average molecular weight of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is preferably 100 to 50,000. A number-average molecular weight of 100 or more can further improve the bending strength and tensile strength of the molded article. A number-average molecular weight of 300 or more is more preferable, 500 or more is even more preferable, and 1,000 or more is most preferable. Furthermore, a number-average molecular weight of 50,000 or less provides a suitably low viscosity of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more, thereby providing excellent impregnation of the reinforcing fibers (A) contained in the molded article and further improving the dispersibility of the reinforcing fibers (A) in the molded article. The number-average molecular weight is more preferably 25,000 or less, even more preferably 15,000 or less, and even more preferably 10,000 or less. The number-average molecular weight of such compounds can be measured using gel permeation chromatography (GPC).

[0139] The content of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more in the composition of the present invention is 0.5 to 30 parts by weight per 100 parts by weight of the total of the carbon fiber (A), the thermoplastic resin (B), and the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more. When the content of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is 0.5 parts by weight or more, the fluidity and dispersibility of the reinforcing fiber (A) in the molded article are further improved. 1 part by weight or more is preferred, and 2 parts by weight or more is even more preferred. On the other hand, when the content of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is 30 parts by weight or less, the tensile strength and impact strength of the molded article can be further improved. 20 parts by weight or less is preferred, 15 parts by weight or less is more preferred, and 10 parts by weight or less is even more preferred.

[0140] The rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more preferably has a heat loss of 5% by weight or less when heated at a rate of 10°C / min (in air) at the molding temperature. This is more preferably 3% by weight or less, and even more preferably 1.5% or less. When the heat loss is 5% by weight or less, the generation of decomposition gases can be suppressed when the resin is impregnated into the reinforcing fibers (A), and the generation of voids can be suppressed during molding. Furthermore, gas generation can be suppressed, particularly during molding at high temperatures.

[0141] Here, the weight loss at the molding temperature of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more can be determined by measuring the weight at the molding temperature by thermogravimetric analysis (TGA) using a platinum sample pan in an air atmosphere at a heating rate of 10°C / min.

[0142] The molded article and molding material of the present invention may contain other components in addition to the components (A) to (C) described above, provided that the object of the present invention is not impaired. Examples of such other components include thermosetting resins, inorganic fillers other than carbon fiber, flame retardants, crystal nucleating agents, ultraviolet absorbers, antioxidants, impact absorbers, vibration dampers, antibacterial agents, insect repellents, deodorizers, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, foam control agents, and coupling agents.

[0143] Next, as a molding method for producing molded articles using a molding material comprising the composition of the present invention, a molding method using a mold is preferred, and various molding methods such as injection molding, extrusion molding, and press molding can be used. In particular, molding methods using an injection molding machine can continuously produce stable molded articles. There are no particular restrictions on the injection molding conditions, but preferred conditions include an injection time of 0.1 to 20 seconds, more preferably 1 to 10 seconds; a back pressure of 0.1 to 20 MPa, more preferably 3 to 15 MPa; a dwell pressure of 1 to 150 MPa, more preferably 5 to 100 MPa; a dwell time of 1 to 30 seconds, more preferably 5 to 20 seconds; a cylinder temperature of 180°C to 350°C; and a mold temperature of 20°C to 160°C. Here, the cylinder temperature refers to the temperature of the part of the injection molding machine where the molding material is heated and melted, and the mold temperature refers to the temperature of the mold into which the resin is injected to form the desired shape. By appropriately selecting these conditions, particularly the injection time, back pressure, and mold temperature, the fiber length of the reinforcing fibers in the molded product can be easily adjusted so as to satisfy the formula [1] described below.

[0144] In the composition of the present invention (in the molding material comprising 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, particularly the bending strength and tensile strength, are further improved. ｗ On the other hand, if the weight average fiber length (Lw) is 7 mm or less, entanglement between the single filaments of the reinforcing fibers (A) is suppressed and dispersibility is further improved, so that the mechanical properties and appearance quality of the molded article are further improved. ｗis more preferably 5 mm or less, and even more preferably 4 mm or less. Here, the "weight average fiber length" in the present invention refers to a weight average fiber length calculated by the following formula, which takes into account the contribution of fiber length, rather than simply taking a number average, by applying the calculation method for weight average molecular weight to the calculation of fiber length. However, the following formula is applied when the fiber diameter and density of the reinforcing fiber (A) are constant. Weight average fiber length = Σ(Mi ２ × Ni) / Σ(Mi × Ni) Mi: fiber length (mm) Ni: number of reinforcing fibers of fiber length Mi

[0145] The weight-average fiber length can be measured by the following method. Using an optical microscope with a hot stage, an appropriate test piece is cut out from the molded product, and the test piece is sandwiched between glass plates on a hot stage set appropriately at 150 to 350 ° C. to match the melting temperature of the thermoplastic resin (B) used. The test piece is then heated in a film-like state and uniformly dispersed. The thermoplastic resin (B) is then observed with an optical microscope (50 to 200 magnification) in a molten state. The fiber lengths of 1,000 randomly selected reinforcing fibers (A) are measured, and the weight-average fiber length (Lw) is calculated from the above formula. Alternatively, a test piece cut out from the molded product is placed in a solvent in which the thermoplastic resin (B) dissolves, and appropriately heated to prepare a solution in which the reinforcing fibers (A) are uniformly dispersed. The solution is then filtered, and the reinforcing fibers (A) dispersed on the filter paper are observed with an optical microscope (50 to 200 magnification). The fiber lengths of 1,000 randomly selected reinforcing fibers (A) are measured, and the weight-average fiber length (Lw) is calculated from the above formula. The filter paper used here may be quantitative filter paper (model number: No. 5C) manufactured by Advantec Co., Ltd.

[0146] Next, the form when the composition of the present invention is used as a molding material will be described. The molding material of the present invention preferably includes a fiber bundle containing continuous reinforcing fibers (A) within a thermoplastic resin (B). A composite may also be included in which a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is filled between each individual fiber of the fiber bundle. The composite is formed by impregnating a fiber bundle with a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more, with the reinforcing fibers (A) dispersed like islands in a sea of ​​the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more. The molding material of the present invention preferably includes a thermoplastic resin (B) on the outer side of the fiber bundle or composite. In a cross section perpendicular to the longitudinal direction of the molding material, the thermoplastic resin (B) is preferably arranged so as to cover the periphery of the fiber bundle or composite, or the fiber bundle or composite and the thermoplastic resin (B) are preferably arranged in layers, with the thermoplastic resin (B) forming the outermost layer.

[0147] When the molding material of the present invention contains a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more, the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more is often low in molecular weight and is typically a relatively brittle, easily crushed solid or liquid at room temperature. By including a thermoplastic resin (B) on the exterior of the composite, the high molecular weight thermoplastic resin (B) protects the composite, suppressing crushing and scattering of the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more due to impact, abrasion, etc. during transportation and handling of the molding material, thereby maintaining the shape of the molding material. From the standpoint of handleability, it is preferable that the molding material of the present invention maintains the aforementioned shape until it is used for molding.

[0148] When the composition of the present invention is used as a molding material, the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more may be contained in any of the raw materials. It may be contained in a fiber bundle or composite, in a thermoplastic resin (B), or in both. For example, a thermoplastic resin composition containing a thermoplastic resin (B) and a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more may be contained in a resin coating a fiber bundle or composite, in a fiber bundle (F) impregnated with a rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more, or in a reinforcing fiber (A) attached to the surface of the reinforcing fiber (A) or contained within a single fiber.

[0149] The composite, the thermoplastic resin (B), and the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more may be in a state where the thermoplastic resin (B) and the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more partially penetrate into part of the composite near the boundary and are compatible with each other, or the fiber bundle may be in a state where the thermoplastic resin (B) and the rosin resin (C) having an acid value and / or hydroxyl value of 100 mgKOH / g or more are impregnated into the fiber bundle.

[0150] When the composition of the present invention is used as a molding material and the molding material contains two types of reinforcing fibers, it is preferable that the two types of reinforcing fibers, for example, carbon fiber and organic fiber or glass fiber, are unevenly distributed in the fiber bundle cross section. Here, the fiber bundle cross section refers to a cross section perpendicular to the longitudinal direction of the fiber bundle. The uneven distribution of carbon fiber and organic fiber or glass fiber in the fiber bundle cross section suppresses entanglement of the carbon fiber and organic fiber or glass fiber during molding, allowing for the production of a molded article in which the carbon fiber and organic fiber or glass fiber are uniformly dispersed. This further improves the mechanical properties of the molded article, particularly the impact strength and appearance quality. Here, in the present invention, "uneven distribution" refers to the carbon fiber and organic fiber or glass fiber being unevenly distributed in part of the fiber bundle cross section, rather than being evenly distributed throughout the entire fiber bundle cross section. For example, examples of "uneven distribution" in the present invention include a so-called core-sheath structure in which, in the cross section of the fiber bundle, carbon fibers are encapsulated within organic fibers or glass fibers, or a structure in which organic fibers or glass fibers are encapsulated within carbon fibers, and a structure in which, in the cross section of the fiber bundle, carbon fiber bundles and organic fiber or glass fiber bundles are present in a state separated by a boundary. In the present invention, "encapsulation" refers to a structure in which carbon fibers are disposed in the core and organic fibers or glass fibers in the sheath, or a structure in which organic fibers or glass fibers are disposed in the core and carbon fibers in the sheath. In the cross section of the fiber bundle, at least a portion of each of the carbon fibers and the organic fibers or glass fibers is in contact with the thermoplastic resin (B) of the outer layer. In this case, the structure in which the carbon fibers, organic fibers, or glass fibers are in contact with the thermoplastic resin (B) also includes a structure in which the carbon fibers, organic fibers, or glass fibers are in contact with the thermoplastic resin (B) via the rosin resin (C) described above.

[0151] In the present invention, a method for confirming that carbon fibers, organic fibers, or glass fibers are unevenly distributed in the fiber bundle may include, for example, observing a cross section of the molding material perpendicular to the longitudinal direction of the fibers using an optical microscope set at a magnification of 300 times, and then processing and analyzing the obtained microscopic image.

[0152] Next, a method for producing the molding material of the present invention will be described. The molding material of the present invention can be obtained by any known production method, including but not limited to the following method. For example, it can be obtained by the following method.

[0153] First, rovings of reinforcing fibers (A) are doubling in parallel with the longitudinal direction of the fibers to produce a fiber bundle containing the reinforcing fibers (A). Next, if necessary, the fiber bundle is impregnated with the molten rosin resin (C) to produce a composite. Furthermore, the fiber bundle or composite is guided into an impregnation die filled with molten thermoplastic resin (B), and a resin composition containing the thermoplastic resin (B) is coated on the outside of the fiber bundle or composite, and the composite is then drawn through a nozzle. After cooling and solidifying, the composite is pelletized to a predetermined length to obtain a molding material. The thermoplastic resin (B) may be impregnated into the fiber bundle as long as it is contained on the outside of the composite.

[0154] Alternatively, a composite may be produced by impregnating the fiber bundle prepared by the above method with the molten rosin resin (C), and the thermoplastic resin (B) may be coated on the outside of the composite. When bonding at least the thermoplastic resin (B) to the surface of a fiber bundle made of reinforcing fibers (A), a preferred bonding method is to place the molten thermoplastic resin (B) in contact with the surface of the fiber bundle and then cool and solidify it. While the bonding method is not particularly limited, more specific examples include a method using an extruder and a coating die for electric wire coating to continuously coat the thermoplastic resin (B) around the fiber bundle, and a method using an extruder and a T-die to apply a molten film-like thermoplastic resin (B) to one or both sides of a fiber bundle flattened by a roll or the like, and then integrating the fiber bundle with a roll or the like.

[0155] 2 and 3 are schematic diagrams showing examples of preferred cross-sectional forms of the molding material of the present invention, in which reference numeral 1 denotes reinforcing fibers (A), reference numeral 2 denotes thermoplastic resin (B), reference numeral 3 denotes rosin resin (C), and reference numeral 4 denotes fiber bundles.

[0156] The cross-sectional shape of the molding material is not limited to that shown in the drawing, as long as the thermoplastic resin (B) is arranged so as to adhere to the outside of the fiber bundles.

[0157] The cross section of the molding material is preferably configured as shown in the longitudinal cross section of FIG. 2, in which the fiber bundle serves as a core material and is sandwiched between layers of thermoplastic resin (B). Also preferred is a configuration in which the fiber bundle serves as a core structure and is surrounded by thermoplastic resin (B) in a core-sheath structure, as shown in the transverse cross section of FIG. 3. A configuration in which multiple fiber bundles are covered by thermoplastic resin (B), as shown in FIG. 4, is also preferred. In this case, the number of fiber bundles is preferably approximately 2 to 6. FIG. 1 is a schematic diagram showing an example of the transverse cross section of a fiber bundle according to the present invention. As shown in FIG. 1, the fiber bundle according to the present invention has rosin resin (C) filled between each individual filament 1 of the reinforcing fiber (A). That is, the individual filaments of the reinforcing fiber (A) are dispersed like islands in a sea of ​​rosin resin (C). In this context, the longitudinal cross section refers to a cross section taken along a plane including the axial direction, and the transverse cross section refers to a cross section taken along a plane perpendicular to the axial direction. Furthermore, when the molding material is cylindrical, such as a pellet, the axial direction refers to the axis of the cylinder.

[0158] The length of the reinforcing fiber (A) and the length of the molding material are substantially the same. This is clear, for example, from the embodiment in Figure 3. In the molding material shown in Figure 3, the individual fibers of the reinforcing fiber (A) are arranged almost parallel to 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 the 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, thereby obtaining better mechanical properties.

[0159] Here, "arranged almost parallel" refers to a state in which the longitudinal axis of the reinforcing fiber (A) and the longitudinal axis of the molding material are oriented 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, and reinforcing fiber (A) significantly shorter than the total length of the molding material is not substantially contained. In particular, the amount of reinforcing fiber (A) shorter than the total length of the molding material is not limited, but the content of reinforcing fiber (A) having a length of 50% or less of the total length of the molding material is preferably 30% by mass or less, more preferably 20% by mass or less, of the total reinforcing fiber (A). By having the reinforcing fiber (A) have substantially the same length as the molding material, the length of the reinforcing fiber (A) in the molded product can be increased, and the tensile strength and impact strength can be further improved. The length of the reinforcing fiber (A) and the molding material is preferably 18 mm or less and 3 mm or more, more preferably 15 mm or less and 5 mm or more. The molding material is preferably continuous, maintaining approximately the same cross-sectional shape in the longitudinal direction.

[0160] Next, an example of a method for producing a molding material according to the present invention will be described. In the present invention, the method for obtaining a fiber bundle by impregnating reinforcing fibers (A) with a rosin resin (C) is not particularly limited, but examples thereof include a method including a step (I) of supplying the rosin resin (C) to the reinforcing fibers (A), contacting the rosin resin (C) (a rosin resin may be blended with another resin. In that case, the other resin is adhered to and impregnated in the reinforcing fibers (A) in the same manner as the rosin resin (C)) with the reinforcing fibers (A) in a molten state at 100 to 300°C, and adhering the rosin resin (C) to the reinforcing fibers (A), and a step (II) of heating the reinforcing fibers (A) to which the rosin resin (C) is adhered, thereby impregnating the reinforcing fibers (A).

[0161] In the above step (I), the method for supplying the rosin resin (C) and adhering it to the reinforcing fibers (A) is not particularly limited, but for example, any method used when applying an oil agent, a sizing agent, or a matrix resin to the reinforcing fibers (A) can be used. Among these, dipping or coating is preferably used.

[0162] Here, dipping refers to a method in which rosin resin (C) is supplied to a molten bath using a pump and reinforcing fibers (A) are passed through the molten bath. Immersing the reinforcing fibers (A) in a molten bath of rosin resin (C) ensures that the rosin resin (C) adheres to the reinforcing fibers (A). Furthermore, coating refers to a method in which the rosin resin (C) is applied to the reinforcing fibers (A) using a coating means such as a reverse roll, a forward rotation roll, a kiss roll, a spray, or a curtain. Here, the reverse roll, forward rotation roll, and kiss roll refer to a method in which molten rosin resin (C) is supplied to a roll using a pump and the molten rosin resin (C) is applied to the reinforcing fibers (A). Furthermore, the reverse roll is a method in which two rolls rotate in opposite directions and the molten rosin resin (C) is applied to the rolls. The forward rotation roll is a method in which two rolls rotate in the same direction and the molten rosin resin (C) is applied to the rolls. Typically, reverse rolls and forward-rotating rolls sandwich the reinforcing fibers (A) between them, and then install additional rolls to ensure the rosin resin (C) is applied. Kiss rolls, on the other hand, are a method of applying the rosin resin (C) simply by contacting the reinforcing fibers (A) with the roll. Therefore, kiss rolls are preferable when the viscosity is relatively low. However, either roll method can be used to apply a predetermined amount of heated, molten rosin resin (C) to the reinforcing fibers (A) by running the reinforcing fibers (A) in contact with the rosin resin (C) per unit length of the fiber. Spraying utilizes the principle of an atomizer, spraying the molten rosin resin (C) in a mist onto the reinforcing fibers (A). Curtain application involves allowing the molten rosin resin (C) to fall naturally through small holes or overflow from a melting tank. The ease of adjusting the amount needed for application minimizes loss of rosin resin (C).

[0163] Furthermore, the melting temperature (temperature in the melting bath) when supplying the rosin resin (C) is preferably 100 to 300°C. If the melting temperature is 100°C or higher, the viscosity of the rosin resin (C) can be appropriately controlled, and uneven adhesion can be suppressed. 150°C or higher is more preferable. On the other hand, if the melting temperature is 300°C or lower, thermal decomposition of the rosin resin (C) can be suppressed even when produced over a long period of time. 250°C or lower is more preferable. By contacting the rosin resin (C) with the reinforcing fibers (A) in a molten state at 100 to 300°C, the rosin resin (C) can be supplied stably.

[0164] Next, the step (step (II)) of heating and impregnating the reinforcing fibers (A) with the rosin resin (C) attached thereto obtained in step (I) will be described. Specifically, this step involves applying tension to the reinforcing fibers (A) with the rosin resin (C) attached thereto with a roll or bar at a temperature at which the rosin resin (C) melts, repeatedly widening and bundling the fibers, or applying pressure or vibration, thereby allowing the rosin resin (C) to penetrate deep into the reinforcing fibers (A). A more specific example is a method of widening the reinforcing fibers (A) by passing them through the surfaces of multiple heated rolls or bars so that they come into contact with each other. Among these, impregnation methods using a cone die, a cone roll, a roll press, or a double belt press are preferably used. Here, the cone die refers to a die whose diameter narrows in the direction of travel, and which bundles the reinforcing fibers (A) while scraping off any excess rosin resin (C) attached thereto and promoting impregnation. The squeeze roll is a roller that applies tension to the reinforcing fibers (A) to scrape off excess rosin resin (C) and promote impregnation. The roll press is a device that continuously removes air from inside the reinforcing fibers (A) by applying pressure between two rolls and promotes impregnation. The double belt press is a device that promotes impregnation by pressing the reinforcing fibers (A) from above and below via belts.

[0165] In step (II), it is preferable that 80 to 100% by weight of the rosin resin (C) supplied is impregnated into the reinforcing fibers (A). Because this directly affects the yield, the higher the impregnation amount relative to the supply amount, the better from the standpoints of economy and productivity. More preferably, it is 85 to 100% by weight, and even more preferably, 90 to 100% by weight. Furthermore, if it is 80% by weight or more, in addition to being economical, it is possible to suppress the generation of volatile components caused by the rosin resin (C) in step (II) and suppress the generation of voids inside the fiber bundle.

[0166] 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 400°C or lower, undesirable side reactions such as decomposition reactions 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 a method using a heated chamber and a method using a hot roller to simultaneously apply heat and pressure.

[0168] In addition, from the viewpoint of suppressing undesirable side reactions such as crosslinking and decomposition of the rosin resin (C), it is preferable to heat the resin in a non-oxidizing atmosphere. Here, a non-oxidizing atmosphere refers to an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, and more preferably an oxygen-free atmosphere, i.e., an inert gas atmosphere such as nitrogen, helium, or argon. In particular, a nitrogen atmosphere is preferable from the viewpoints of economy and ease of handling.

[0169] Furthermore, the reinforcing fiber (A) bundle may be opened in advance before the steps (I) and (II). Opening is an operation of separating the converged reinforcing fiber bundle, and is expected to have the effect of further increasing the impregnation of the rosin resin (C). Opening reduces the thickness of the reinforcing fiber bundle, and when the width of the reinforcing fiber bundle before opening is b1 (mm) and the thickness is a1 (μm), and the width of the reinforcing fiber bundle after opening is b2 (mm) and the thickness is a2 (μm), the opening ratio = (b2 / a2) / (b1 / a1) is preferably 2.0 or more, and more preferably 2.5 or more.

[0170] The method for spreading the reinforcing fiber bundle is not particularly limited, and examples that can be used include a method of alternately passing the reinforcing fiber bundle through concave and convex rolls, a method using a drum-shaped roll, a method of adding tension fluctuations to axial vibrations, a method of varying the tension of the reinforcing fiber bundle using two friction bodies that reciprocate vertically, and a method of blowing air onto the reinforcing fiber bundle.

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

[0172] Alternatively, a molding material mixture may be obtained by dry-blending a molding material obtained by coating the fiber bundles prepared by the above method with a thermoplastic resin (B) with pellets obtained by melt-kneading the thermoplastic resin (B). In this case, the content of the reinforcing fiber (A) in the molded product can be easily adjusted. Alternatively, a molding material mixture may be obtained by pellet-blending a molding material obtained by coating a composite of carbon fiber and the rosin resin (C) with a thermoplastic resin (B) with a molding material obtained by coating a composite of organic fiber or glass fiber and the rosin resin (C) with a thermoplastic resin (B). Unlike melt-kneading, dry-blending refers to stirring and mixing multiple materials at a temperature at which the resin components do not melt to produce a substantially homogeneous mixture. This method is preferably used when using pellet-shaped molding materials, such as for injection molding or extrusion molding.

[0173] The molding material mixture preferably includes a carbon fiber-reinforced thermoplastic resin molding material (X) (sometimes referred to as "carbon fiber-reinforced molding material") containing at least carbon fiber, thermoplastic resin (B), and the 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") containing at least organic fiber or glass fiber, thermoplastic resin (B), and the rosin resin (C). The carbon fiber-reinforced molding material (X) preferably includes a composite formed by impregnating carbon fiber with the rosin resin (C), and the thermoplastic resin (B) is disposed on the outer surface of the composite. The carbon fiber length and the carbon fiber-reinforced thermoplastic resin molding material length are preferably substantially the same. The organic fiber / or glass fiber-reinforced molding material (Y) preferably includes a composite formed by impregnating organic fiber or glass fiber with the rosin resin (C), and the thermoplastic resin (B) is disposed on the outer surface of the composite. The rosin resins (C) and the thermoplastic resins (B) may be the same.

[0174] The composition of the present invention is a fiber-reinforced thermoplastic resin composition having excellent tensile strength, impact strength, and appearance quality. Applications of molded articles and molding materials comprising the composition of the present invention include electrical and electronic devices, home appliances, housings, automotive parts, and parts for sports applications. Examples of electrical and electronic device housings and parts include electronic device housings for computers, televisions, video players, DVD players, cameras, audio equipment, connectors, speakers, microphones, headphones, small motors, and computer-related parts. Examples of home appliances include VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audiovisual equipment parts such as laser discs (registered trademark), compact discs, and DVDs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, and word processor parts. Examples of optical and precision machinery-related parts include office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, binoculars, cameras, and watches. Examples of automotive parts and vehicle-related parts include door pads, pillars, console boxes, various motor housings, roof rails, fenders, garnishes, bumpers, door panels, roof panels, hood panels, trunk lids, door mirror stays, spoilers, hood louvers, wheel covers, hubcaps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, wipers, etc. The composition of the present invention is also suitable as sporting goods, and is suitably used for golf-related goods such as golf clubs, shafts, grips, and golf balls, racket sports-related goods such as tennis rackets, tennis balls, badminton rackets, their strings, and badminton shuttlecocks, personal protective equipment for sports such as masks, helmets, breastplates, elbow pads, and knee pads for American football, baseball, softball, etc., shoe-related goods such as soles for sports shoes, fishing tackle-related goods such as fishing rods, reels, and lures, summer sports-related goods such as surfing, winter sports-related goods such as skiing and snowboarding, and other indoor and outdoor sports-related goods.

[0175] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the descriptions of these examples. First, the methods for evaluating various properties used in the examples will be described.

[0176] (1) Weight average fiber length Test pieces cut out from the molded product were placed in a solvent in which the thermoplastic resin (B) used in each example and comparative example was dissolved, and then heated appropriately to obtain a solution in which the reinforcing fibers (A) were uniformly dispersed. Then, using quantitative filter paper (No. 5C) manufactured by Advantec Co., Ltd., the solution was filtered and the reinforcing fibers (A) dispersed on the filter paper were observed under an optical microscope (50 to 200 times). The fiber lengths of 1,000 randomly selected reinforcing fibers (A) were measured, and the weight average fiber length (Lw) was calculated using the following formula. Average fiber length = Σ (Mi ２ × Ni) / Σ(Mi × Ni) Mi: fiber length (mm) Ni: number of fibers with fiber length Mi

[0177] (2) Measurement of tensile strength of molded product The ISO dumbbell test pieces obtained in each example and comparative example were subjected to a tensile test at a tensile speed of 5 mm / min using a tensile tester Autograph AG-20kNX (manufactured by Shimadzu Corporation) in accordance with ISO 527 (2012), and the maximum point stress was determined.

[0178] (3) Measurement of Charpy impact strength of molded products A parallel portion was cut out from the ISO dumbbell test specimen obtained in each example and comparative example, and a V-notched Charpy impact test was carried out in accordance with ISO 179 using a C1-4-01 model testing machine manufactured by Tokyo Testing Machine Co., Ltd., to measure the impact strength (kJ / cm ２ ) was calculated.

[0179] (4) Measurement of Acid Value / Hydroxyl Value of Rosin Resin (C) The acid value / hydroxyl value of the sample to be measured was measured in accordance with JIS K 0070.

[0180] (5) Measurement of Thermal Weight Loss of Rosin Resin (C) The sample was measured by thermogravimetric analysis (TGA). Using a platinum sample pan, the measurement was carried out in a nitrogen atmosphere at a temperature increase rate of 10°C / min, and the weight loss rate at 270°C was measured.

[0181] (6) Appearance evaluation of molded articles (blackness evaluation) For test pieces of 80 mm x 80 mm x 3 mm thickness obtained in each example and comparative example, L* in the appearance of the molded article surface was measured using a spectrocolorimeter (SD7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). Measurements were performed three times, and the average value was used for the evaluation of each example and comparative example. Evaluation was made according to the following criteria, with A and B being considered as passing. A: L* is less than 18 B: L* is less than 20 C: L* is 20 or more

[0182] (7) Appearance evaluation of molded articles (fiber dispersion evaluation) The number of undispersed CF bundles present on the front and back surfaces of the test pieces for measuring drop weight impact strength obtained in each Example and Comparative Example was visually counted. Evaluation was carried out on 50 molded articles, and the fiber dispersion of the total number was judged according to the following criteria, with A and B being considered as passing. A: Less than 1 undispersed CF bundle B: 1 or more undispersed CF bundles C: 2 or more undispersed CF bundles

[0183] Reference Example 1: Preparation of Carbon Fiber (A-1) A copolymer containing polyacrylonitrile as the main component was spun, baked, and surface-oxidized to obtain a carbon fiber having a total of 24,000 single fibers, a single fiber diameter of 7 μm, a mass per unit length of 1.6 g / m, and a specific gravity of 1.8 g / cm. ３ and a surface oxygen concentration ratio [O / C] of 0.2, resulting in continuous carbon fibers. 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 solution was prepared by dissolving glycerol polyglycidyl ether as a polyfunctional compound in water to a concentration of 2 wt %, and the sizing agent was applied to the carbon fibers by a dipping method, followed by drying at 230°C. The amount of sizing agent attached to the carbon fibers thus obtained was 1.0 wt %.

[0184] Production Example 1 Preparation of Rosin Resin (C-2) A reactor equipped with a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 100 parts of hydrogenated rosin and heated under a nitrogen stream until completely melted. 190 parts of bisphenol A polymer epoxy resin (epoxy equivalent: 500) was then added with stirring, and 0.1 parts of 2-methylimidazole was added at 140°C. The mixture was allowed to react at 180°C for 3 hours to obtain a rosin resin (C-2) with a hydroxyl value of 150 mg / KOH / g.

[0185] Production Example 2: Preparation of Rosin Resin (C-3) A reactor equipped with a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 100 parts of hydrogenated rosin and heated under a nitrogen stream until completely melted. 230 parts of bisphenol A polymer epoxy resin (epoxy equivalent: 500) was then added with stirring, and 0.1 parts of 2-methylimidazole was added at 140°C. The mixture was allowed to react at 180°C for 3 hours to obtain a rosin resin (C-3) with a hydroxyl value of 200 mg / KOH / g.

[0186] Production Example 3: Preparation of Rosin Resin (C-5) A reactor equipped with a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 200 parts of disproportionated rosin and heated under a nitrogen stream until completely melted. Then, 109 parts of bisphenol A polymer epoxy resin (epoxy equivalent: 180) was added with stirring, and 0.06 parts of 2-methylimidazole was added at 140°C. The mixture was allowed to react for 5 hours at 150°C, yielding a rosin polyol with a hydroxyl value of 125 mgKOH / g. Subsequently, 112 parts of Chinese gum rosin was added, and the mixture was allowed to react for 2 hours at 275°C, yielding a rosin resin (C-5) with a hydroxyl value of 43 mgKOH / g.

[0187] Production Example 4: Preparation of Rosin Resin (C-6) A reactor equipped with a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 200 parts of disproportionated rosin and heated under a nitrogen stream until completely melted. Then, 109 parts of bisphenol A polymer epoxy resin (epoxy equivalent: 180) was added with stirring, and 0.06 parts of 2-methylimidazole was added at 140°C. The mixture was allowed to react for 5 hours at 150°C, yielding a rosin polyol with a hydroxyl value of 125 mgKOH / g. Subsequently, 56 parts of Chinese gum rosin was added, and the mixture was allowed to react for 2 hours at 275°C, yielding a rosin resin (C-6) with a hydroxyl value of 75 mgKOH / g.

[0188] Organic Fiber (A-2) Liquid crystal polyester fiber ("Scivelas" (registered trademark) 1700T-288f, manufactured by Toray Industries, Inc., strength: 23.5 cN / dtex, melting point: 330°C, energy propagation speed: 17.3 km / s) was used.

[0189] Glass Fiber (A-3) A glass fiber roving (manufactured by Asahi Fiber Co., Ltd., "ER2220", fiber diameter: 16 μm, aminosilane coupling agent, olefin emulsion used, number of filaments: about 4000) was used.

[0190] Thermoplastic Resin (B) (B-1) A polyamide resin (manufactured by Toray Industries, Inc., nylon 6 resin "Amilan" (registered trademark) CM1001) was used.

[0191] (B-2) Polyamide resin (manufactured by Toray Industries, Inc., nylon 610 resin "Amilan" (registered trademark) CM2001) was used.

[0192] (B-3) Polyamide resin (manufactured by Arkema, nylon 11 resin "Rilsan" (registered trademark) BMN0" was used.

[0193] (B-4) Polyamide resin (manufactured by Arkema Co., Ltd., nylon 12 resin "Lilsamid" (registered trademark) AMN0" was used.

[0194] (B-5) Polyamide resin (manufactured by Kuraray Co., Ltd., nylon 9T resin "Genestar" (registered trademark) N1000A") was used.

[0195] (B-6) A pellet blend of polypropylene resin (Prime Polypro (registered trademark) J137 manufactured by Prime Polymer Co., Ltd.) and maleic acid-modified polypropylene resin (Admer (registered trademark) QE840 manufactured by Mitsui Chemicals, Inc.) in a weight ratio of 85 / 15 was used.

[0196] (B-7) Polycarbonate resin (manufactured by Teijin Chemicals Ltd., "Panlite" (registered trademark) L-1225L) was used.

[0197] (B-8) Polyarylene sulfide resin (manufactured by Toray Industries, Inc., PPS resin "TORELINA" (registered trademark) M2888") was used.

[0198] Thermoplastic Resin (Ba) (Ba-1) A polyamide resin (manufactured by Toray Industries, Inc., nylon 6 resin "Amilan" (registered trademark) CM1001) was used.

[0199] (Ba-2) Polyamide resin (manufactured by Arkema, nylon 12 resin "Lilsamid" (registered trademark) AMN 0" was used.

[0200] Resin (Bb) having a reactive functional group (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 (manufactured by Mitsui Chemicals, Inc.).

[0203] Rosin Resin (C) (C-1) Highly polar rosin: (Arakawa Chemical Industries, Ltd.'s "Pine Crystal" D-6011 (registered trademark), hydroxyl value 100 mg KOH / g, heat loss at 270°C: 1.8%) was used.

[0204] (C-2) The rosin resin (C-2) obtained in Production Example 1 (heat loss at 270°C: 1.4%) was used.

[0205] (C-3) The rosin resin (C-3) obtained in Production Example 2 (loss on heat at 270°C: 0.8%) was used.

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

[0207] (C-5) The rosin resin (C-5) obtained in Production Example 3 (heat loss at 270°C: 1.6%) was used.

[0208] (C-6) The rosin resin (C-6) obtained in Production Example 4 (heat loss at 270°C: 2.2%) was used.

[0209] Resins (D) used in Comparative Examples (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 resin (Yasuhara Chemical Co., Ltd., "Clearon M105 (trade name)", acid value 0 mg KOH / g, heat loss at 270 ° C: 7.5%) was used.

[0211] (D-3) Petroleum resin (manufactured by Idemitsu Kosan Co., Ltd., "Imarv P-100 (trade name)", hydroxyl value and acid value both less than 1 mgKOH / g, heat loss at 270°C: 7.0%) was used.

[0212] Example 1 A long fiber reinforced resin pellet manufacturing apparatus equipped with a coating die for the electric wire coating method attached to the tip of a TEX-30α type twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) (screw diameter 30 mm, L / D = 32) was used. The extruder cylinder temperature was set to 260°C, and the thermoplastic resin (B-1) described above was fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The rosin resin (C-1) heated and melted at 200°C was discharged in an amount of 4 parts by weight per 100 parts by weight of (A) to (C). The resin was applied to a fiber bundle consisting of carbon fiber (A-1), and then fed into a die opening (diameter 3 mm) from which the molten thermoplastic resin (B-1) was discharged. The resin was continuously arranged so as to coat the periphery of the carbon fiber (A-1). At this time, the internal cross section of the fiber bundle showed that at least a portion of the carbon fiber (A-1) was in contact with the thermoplastic resin (B-1). The obtained strand was cooled and then cut with a cutter to a pellet length of 7 mm to obtain long fiber pellets. At this time, the take-up speed was adjusted so that the carbon fiber (A-1) was 20 parts by weight per 100 parts by weight of the total of (A) to (C). The length of the carbon fiber (A-1) in the obtained long fiber pellets was substantially the same as the pellet length.

[0213] The long fiber pellets thus obtained were injection molded using an injection molding machine (J110AD, manufactured by The Japan Steel Works, Ltd.) under the following conditions: injection time: 2 seconds, back pressure: 5 MPa, dwell pressure: 40 MPa, dwell time: 10 seconds, cylinder temperature: 260°C, and mold temperature: 60°C. This resulted in the production of molded articles: ISO dumbbell test pieces and 80 mm x 80 mm x 3 mm thick test pieces for color tone evaluation and dispersibility evaluation. Here, the cylinder temperature refers to the temperature of the part of the injection molding machine where the molding material is heated and melted, and the mold temperature refers to the temperature of the mold into which the resin is injected to form the desired shape. The obtained test pieces (molded articles) were left to stand for 24 hours in a constant temperature and humidity chamber adjusted to a temperature of 23°C and 50% RH, after which their properties were evaluated. The evaluation results obtained using the above-mentioned methods are summarized in Table 1.

[0214] Examples 2 to 9 Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the type of rosin resin used was changed as shown in Table 1. The evaluation results are summarized in Table 1.

[0215] (Examples 10 to 18) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratios or the types of resins and rosin resins used were changed as shown in Tables 1 and 2, and the cylinder temperature was set to 230° C. The evaluation results are summarized in Tables 1 and 2.

[0216] Example 19 A molded article was produced and evaluated in the same manner as in Example 1, except that the back pressure during injection molding was changed to 20 MPa. The evaluation results are shown in Table 2.

[0217] Example 20 A molded article was produced and evaluated in the same manner as in Example 1, except that the molding back pressure during injection molding was changed to 15 MPa. The evaluation results are shown in Table 2.

[0218] Example 21 A molded article was produced and evaluated in the same manner as in Example 1, except that the molding back pressure during injection molding was changed to 3 MPa. The evaluation results are shown in Table 2.

[0219] Example 22 A molded article was produced and evaluated in the same manner as in Example 1, except that the molding back pressure during injection molding was changed to 1 MPa. The evaluation results are shown in Table 2.

[0220] (Examples 23 and 24) A long fiber reinforced resin pellet manufacturing apparatus equipped with a coating die for the wire coating method installed at the tip of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D = 32) manufactured by The Japan Steel Works, Ltd. was used, the extruder cylinder temperature was set to 260 ° C., and the thermoplastic resin (B-1) described above was fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The rosin resin (C-2) heated and melted at 200 ° C. was adjusted to a discharge amount of 4 parts by weight per 100 parts by weight of (A) to (C). The rosin resin was applied to a fiber bundle consisting of a fiber bundle consisting of carbon fiber (A-1) and organic fiber (A-2). The melted thermoplastic resin (B-1) was then fed to a die opening (diameter 3 mm) from which the thermoplastic resin was discharged, and the carbon fiber (A-1) and the organic fiber (A-2) were continuously coated. The carbon fiber (A-1) and the organic fiber (A-2) were unevenly distributed in the internal cross section of the composite fiber bundle (E). The uneven distribution was such that at least a portion of the carbon fiber (A-1) and the organic fiber (A-2) were in contact with the thermoplastic resin (B-1). The resulting strand was cooled and then cut with a cutter to a pellet length of 7 mm to obtain long fiber pellets. The take-up speed was adjusted so that the carbon fiber (A-1) was 20 parts by weight per 100 parts by weight of the total of (A) to (C). The lengths of the carbon fiber (A-1) and the organic fiber (A-2) in the obtained long fiber pellets were substantially the same as the pellet length. A molded article was produced and evaluated in the same manner as in Example 1, except that long fiber pellets were used. The evaluation results are summarized in Table 2.

[0221] Examples 25 and 26 Molded articles were produced and evaluated in the same manner as in Example 23, except that the composition ratio or the type of fiber used was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0222] (Examples 27 and 34) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the types of resins and rosin resins used were changed as shown in Table 3 and the cylinder temperature was set to 240° C. The evaluation results are summarized in Table 3.

[0223] (Examples 28 and 35) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the types of resins and rosin resins used were changed as shown in Table 3, and the cylinder temperature was set to 270° C. and the mold temperature was set to 80° C. The evaluation results are summarized in Table 3.

[0224] (Example 29) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratios or the types of resins and rosin resins used were changed as shown in Table 3, and the cylinder temperature was set to 330°C and the mold temperature to 140°C. The evaluation results are summarized in Table 3.

[0225] (Example 30) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the types of resins and rosin resins used were changed as shown in Table 3, and the cylinder temperature was set to 280° C. and the mold temperature was set to 100° C. The evaluation results are summarized in Table 3.

[0226] (Example 31) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the types of resins and rosin resins used were changed as shown in Table 3 and the cylinder temperature was set to 200° C. The evaluation results are summarized in Table 3.

[0227] (Example 32) Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratios or the types of resins and rosin resins used were changed as shown in Table 3, and the cylinder temperature was set to 320°C and the mold temperature to 130°C. The evaluation results are summarized in Table 3.

[0228] Example 33 Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the type of rosin resin used was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0229] Example 36 Molded articles were produced and evaluated in the same manner as in Example 10, except that the composition ratios or the types of resins and rosin resins used were changed as shown in Table 3. The evaluation results are summarized in Table 3.

[0230] (Example 37) (Manufactured by The Japan Steel Works, Ltd.) TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D = 32) equipped with a coating die for the wire coating method installed at the tip of the extruder cylinder temperature was set to 270 ° C., and the above-mentioned thermoplastic resin (Ba-1) and resin (Bb-1) having a reactive functional group were fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The rosin resin (C-1) heated and melted at 200 ° C. was adjusted to a discharge amount of 4 parts by weight relative to a total of 100 parts by weight of (A) to (C), and then applied to a fiber bundle made of carbon fiber (A-1). The molten thermoplastic resin (Ba-1) and resin (Bb-1) having a reactive functional group were fed to a die opening (diameter 3 mm) that discharged the molten resin, and the carbon fiber (A-1) was continuously arranged so as to cover the periphery. At this time, at least a portion of the carbon fiber (A-1) in the internal cross section of the fiber bundle was in contact with the thermoplastic resin (Ba-1) and the resin (Bb-1) having a reactive functional group. The obtained strand was cooled and then cut with a cutter to a pellet length of 7 mm to obtain long fiber pellets. At this time, the take-up speed was adjusted so that the carbon fiber (A-1) was 20 parts by weight per 100 parts by weight of the total of (A) to (C). The length of the carbon fiber (A-1) in the obtained long fiber pellets was substantially the same as the pellet length.

[0231] The long fiber pellets thus obtained were injection molded using an injection molding machine (J110AD, manufactured by The Japan Steel Works, Ltd.) under the following conditions: injection time: 2 seconds, back pressure: 5 MPa, dwell pressure: 40 MPa, dwell time: 10 seconds, cylinder temperature: 270°C, and mold temperature: 80°C. This produced molded ISO dumbbell test pieces and 80 mm x 80 mm x 3 mm thick test pieces for color tone evaluation and dispersibility evaluation. Here, the cylinder temperature refers to the temperature of the part of the injection molding machine where the molding material is heated and melted, and the mold temperature refers to the temperature of the mold into which the resin is injected to form the desired shape. The obtained test pieces (molded products) were left to stand for 24 hours in a constant temperature and humidity chamber adjusted to a temperature of 23°C and 50% RH before being subjected to property evaluation. The evaluation results obtained using the above-mentioned methods are summarized in Table 4.

[0232] (Examples 38 to 47, 49, 50 and 59) Molded articles were produced and evaluated in the same manner as in Example 37, except that the composition ratios or the types of resins and rosin resins used were changed as shown in Tables 4 and 5. The evaluation results are summarized in Tables 4 and 5.

[0233] (Example 48) Molded articles were produced and evaluated in the same manner as in Example 37, except that the composition ratio or the types of resins and rosin resins used were changed as shown in Table 4, and the cylinder temperature was set to 230°C and the mold temperature to 60°C. The evaluation results are summarized in Table 4.

[0234] Example 55 A molded article was produced and evaluated in the same manner as in Example 1, except that the back pressure during injection molding was changed to 20 MPa. The evaluation results are shown in Table 2.

[0235] Example 56 A molded article was produced and evaluated in the same manner as in Example 37, except that the back pressure during injection molding was changed to 15 MPa. The evaluation results are shown in Table 5.

[0236] Example 57 A molded article was produced and evaluated in the same manner as in Example 37, except that the molding back pressure during injection molding was changed to 3 MPa. The evaluation results are shown in Table 5.

[0237] Example 58 A molded article was produced and evaluated in the same manner as in Example 37, except that the molding back pressure during injection molding was changed to 1 MPa. The evaluation results are shown in Table 5.

[0238] (Examples 51 and 52) A long fiber reinforced resin pellet manufacturing apparatus equipped with a coating die for the wire coating method installed at the tip of a TEX-30α type twin-screw extruder (screw diameter 30 mm, L / D = 32) manufactured by The Japan Steel Works, Ltd. was used, the extruder cylinder temperature was set to 270 ° C., and the above-described thermoplastic resin (Ba-1) and the resin (Bb-1) having a reactive functional group were fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The rosin resin (C-2) heated and melted at 200 ° C. was adjusted to a discharge amount of 4 parts by weight relative to a total of 100 parts by weight of (A) to (C), and then applied to a fiber bundle consisting of a fiber bundle consisting of carbon fiber (A-1) and organic fiber (A-2). The molten thermoplastic resin (B-1) was supplied to a die opening (diameter 3 mm) that discharges the resin, and the carbon fiber (A-1) and the organic fiber (A-2) were continuously arranged so as to coat the periphery thereof. The internal cross section of the composite fiber bundle (E) at this time showed uneven distribution of the carbon fiber (A-1) and the organic fiber (A-2). The uneven distribution was such that at least a portion of the carbon fiber (A-1) and the organic fiber (A-2) were in contact with the thermoplastic resin (Ba-1) and the resin (Bb-1) having a reactive functional group. The resulting strand was cooled and then cut into pellets with a length of 7 mm using a cutter to obtain long fiber pellets. The take-up speed was adjusted so that the carbon fiber (A-1) was 20 parts by weight per 100 parts by weight of the total of (A) to (C). The lengths of the carbon fiber (A-1) and the organic fiber (A-2) in the obtained long fiber pellets were substantially the same as the pellet length. A molded article was produced and evaluated in the same manner as in Example 37, except that long fiber pellets were used. The evaluation results are summarized in Table 5.

[0239] (Examples 53, 54, and 60) Molded articles were produced and evaluated in the same manner as in Example 51, except that the composition ratio or the type of fiber and type of rosin resin used were changed as shown in Table 2. The evaluation results are summarized in Table 5.

[0240] Comparative Examples 1 to 9 Molded articles were produced and evaluated in the same manner as in Example 1, except that the composition ratio or the type of rosin resin used was changed as shown in Table 6. The evaluation results are summarized in Table 6.

[0241] Comparative Example 10 A molded article was produced and evaluated in the same manner as in Example 1, except that the molding back pressure during injection molding was changed to 40 MPa. The evaluation results are shown in Table 6.

[0242] Comparative Example 11 A molded article was produced and evaluated in the same manner as in Example 4, except that the pellet length was changed to 14 mm. The evaluation results are shown in Table 6.

[0243] All of the materials in Examples 1 to 9 exhibited excellent dispersibility and high tensile strength, impact strength, and excellent appearance quality, particularly blackness. The materials in Examples 10 to 18 and 27 to 36, which used different resin types and rosin resin types, also exhibited excellent dispersibility and high tensile strength, impact strength, and excellent appearance quality, particularly blackness. The same excellent effects were also observed when the fiber length in the molded articles in Examples 19 to 22 was changed. Examples 23 to 26, which contained organic fiber (A-2) or glass fiber (A-3), also exhibited similarly excellent effects, and further showed excellent impact strength.

[0244] All of the materials in Examples 37 to 45 exhibited excellent dispersibility, high mechanical strength, especially impact strength, and excellent appearance quality, especially blackness. The materials in Examples 46 to 50 and Example 59, in which the resin type and rosin resin type were changed, also exhibited excellent dispersibility, high mechanical strength, especially impact strength, and excellent appearance quality, especially blackness. The same excellent effects were also exhibited when the fiber length in the molded articles in Examples 55 to 58 was changed. Examples 51 to 54 and 60, which contained organic fiber (A-2) or glass fiber (A-3), also exhibited excellent effects, and furthermore, showed excellent effects in impact strength.

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

[0246] In Comparative Example 6, the amount of reinforcing fibers was small, resulting in a weak fiber reinforcement effect and poor tensile strength and impact strength. In Comparative Example 7, the amount of reinforcing fibers was excessive, resulting in the reinforcing fibers becoming entangled and fiber breakage occurring within the molded product, resulting in insufficient dispersibility and poor impact strength. In Comparative Example 8, the amount of rosin resin relative to the reinforcing fibers was small, resulting in insufficient wettability between the reinforcing fibers and the thermoplastic resin, resulting in poor tensile strength, impact strength, and appearance quality, particularly blackness. In Comparative Example 9, the amount of rosin resin was excessive, resulting in a decrease in the strength and toughness of the thermoplastic resin, resulting in poor tensile strength and impact strength of the molded product. In Comparative Example 10, the fiber length of the reinforcing fibers was short, resulting in a weak fiber reinforcement effect and poor tensile strength and impact strength. In Comparative Example 11, the pellet length, i.e., the fiber length, was too long, resulting in insufficient dispersibility and poor appearance quality, particularly blackness.

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[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 and electronic devices, office automation equipment, home appliances, housings, sports components, automobile parts, and the like.

[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 a hydroxyl value of 100 mgKOH / g or more, and the thermal weight loss of the rosin resin (C) at 270 °C is less than 5%.

2. The fiber-reinforced thermoplastic resin composition according to Claim 1, comprising 1 to 100 parts by weight of rosin resin (C) with respect to 100 parts by weight of the reinforcing fiber (A).

3. The fiber-reinforced thermoplastic resin composition according to Claim 1, wherein the rosin resin (C) is modified.

4. The fiber-reinforced thermoplastic resin composition according to Claim 1, wherein the rosin resin (C) contains 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 according to Claim 1, wherein the reinforcing fiber (A) further contains at least one selected from the group consisting of organic fiber and glass fiber.

6. The fiber-reinforced thermoplastic resin composition according to Claim 5, wherein the organic fiber is at least one selected from the group consisting of polyamide fiber, polyester fiber, liquid crystal polyester fiber, polyarylene sulfide fiber, and fluororesin fiber.

7. The fiber-reinforced thermoplastic resin composition according to any one 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 according to Claim 7, wherein the thermoplastic resin (B) contains at least one selected from the group consisting of polyamide resin, polyolefin resin, polycarbonate resin, and polyphenylene sulfide resin.

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

10. The thermoplastic resin (Bb) is composed of a thermoplastic resin having a reactive functional group, and contains 20 to 94.5 parts by weight of a melt-kneaded resin composition (B1) obtained by melt-kneading the thermoplastic resin (Ba) and the thermoplastic resin (Bb). The melt-kneaded resin composition (B1) contains a compound (Bc) generated by the reaction of the thermoplastic resin (Ba) and the resin (Bb) having a reactive functional group with the resin (Ba) and the resin (Bb). In the melt-kneaded resin composition (B1), the resin (Bb) having a reactive functional group is dispersed in the thermoplastic resin (Ba) in a particulate form with a number average particle diameter of 10 to 1,000 nm. The fiber-reinforced thermoplastic resin composition according to claim 9.

11. In the fiber-reinforced thermoplastic resin composition according to claim 10, the thermoplastic resin (Ba) contained in the melt-kneaded resin composition (B1) forms a continuous phase, the resin (Bb) having a reactive functional group forms a dispersed phase, and the dispersed phase contains fine particles having a particle diameter of 1 to 100 nm and composed of the compound (Bc).

12. The fiber-reinforced thermoplastic resin composition according to claim 11, wherein the area ratio of the fine particles composed of the compound (Bc) in the dispersed phase composed of the resin (Bb) is 20% or more.

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

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

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