Fiber-reinforced resin molded article and molding material

Abstract

This fiber-reinforced resin molded article contains carbon fibers (A) and a thermoplastic resin (B), and is characterized in that the carbon fibers (A) are contained at a quantity of 5-40 parts by weight relative to a total of 100 parts by weight of the carbon fibers (A) and the thermoplastic resin (B), and that the carbon fibers (A) are such that 1000 carbon fibers (A) randomly selected from a molded article have a long / short ratio of fiber length, as expressed by formula 1, of 2-20. Long / short ratio of fiber length=Σ(L0.6) / Σ(L0.1)···(Formula 1). L0.66 denotes the length (mm) of fibers having a fiber length of 0.6 mm or more, and L0.1 denotes the length (mm) of fibers having a fiber length of 0.1 mm or less. The present invention is capable of providing: a fiber-reinforced resin molded article which exhibits excellent fluidity and mechanical characteristics and also exhibits excellent aesthetic quality; and a fiber-reinforced resin molding material that can realize this molded article.

Description

Fiber-reinforced resin molded products and molding materials

[0001] The present invention relates to a molded article containing carbon fiber as a reinforcing fiber and a thermoplastic resin, and to a molding material containing carbon fiber and a thermoplastic resin.

[0002] Fiber-reinforced resins, which are made from reinforcing fibers and thermoplastic resins, are widely used in various industrial applications due to their light weight and excellent mechanical properties. In particular, molded products made from pelletized molding materials using economical and productive molding methods such as injection molding and stamping molding are frequently used for parts and housings of automotive equipment, personal computers, office automation equipment, audiovisual equipment, mobile phones, telephones, home appliances, and toys.

[0003] In particular, fiber-reinforced resins that use carbon fiber as the reinforcing fiber are frequently used when high levels of lightness and mechanical properties are required, because the excellent specific strength of carbon fiber allows them to exhibit high tensile strength and elastic modulus despite their light weight.

[0004] Patent Document 1 discloses a molded article with excellent mechanical properties obtained by injection molding long-fiber-reinforced thermoplastic resin pellets containing at least reinforcing fibers having substantially the same length as the pellets. Patent Documents 2, 3, and 4 disclose that a molded article with improved mechanical properties and appearance quality can be obtained by injection molding thermoplastic resin pellets in which two types of reinforcing fibers, one having a long fiber length and the other having a short fiber length, are combined with a thermoplastic resin.

[0005] JP 10-138379 A JP 2006-181776 A JP 2018-162337 A JP 10-138244 A

[0006] However, in recent years, molded products have become smaller, thinner, and more complex, which has led to a demand for high moldability in molding materials, and a high level of balance between excellent fluidity and mechanical properties that can accommodate small, thin, and complex shapes.

[0007] Traditionally, fiber-reinforced resin molding materials containing reinforcing fibers have tended to have a decreased fluidity in correlation with the improvement in mechanical properties due to fiber length. Carbon fiber, in particular, exhibits superior specific strength and specific modulus compared to other reinforcing fibers such as glass fiber, but its generally small fiber diameter tends to cause fiber interference during molding, making it difficult to improve fluidity. However, in order to achieve ever smaller, thinner, and more complex shapes in molded products, molded products that exhibit even better fluidity than before while maintaining high mechanical properties are required.

[0008] In view of the above problems and needs, the object of the present invention is to provide a fiber-reinforced resin molded product that has both excellent fluidity and mechanical properties and also has excellent appearance quality, and a fiber-reinforced resin molding material that realizes this.

[0009] In order to solve the above problems, the present invention has the following configuration: (1) A fiber-reinforced resin molded product containing carbon fibers (A) and a thermoplastic resin (B), wherein the carbon fibers (A) are contained in an amount of 5 to 40 parts by weight per 100 parts by weight of the total of the carbon fibers (A) and the thermoplastic resin (B), and the carbon fibers (A) are characterized in that 1,000 carbon fibers (A) randomly selected from the molded product have a long-to-short fiber length ratio of 2 to 20 as shown in the following formula 1: Long-to-short fiber length ratio=Σ(L ０．６ ) / Σ(L ０．１ )...(Formula 1) L ０．６ : Length (mm) of fibers having a fiber length of 0.6 mm or more ０．１ : Length (mm) of fibers having a fiber length of 0.1 mm or less Furthermore, Equation 1 can be transformed into the following Equation 1-2: Fiber length ratio = Σ(M ０．６ ×N ０．６ ) / Σ(M ０．１ ×N ０．１ ) ... (Formula 1-2) M ０．６ : Length (mm) of fibers having a length of 0.6 mm or more ０．６ : Number of fibers having each length for fibers having a length of 0.6 mm or more M ０．１ : Length (mm) of each fiber having a length of 0.1 mm or less N ０．１: The number of fibers having each length for fibers having a length of 0.1 mm or less. (2) The fiber reinforced resin molded product according to (1), characterized in that 1000 carbon fibers (A) randomly selected from the molded product have a short fiber ratio of 15% or less as shown in the following formula 2. Short fiber ratio = Σ(L ０．１ ) / Σ(Li)×100(%)...(Formula 2) L ０．１ : Length of fibers having a fiber length of 0.1 mm or less (mm) Li: Fiber length of each fiber (mm) Furthermore, Equation 2 can be transformed into the following Equation 2-2. Short fiber ratio = Σ(M ０．１ ×N ０．１ ) / Σ(Mi×Ni)×100(%) ...(Formula 2-2) M ０．１ N: Length of fibers of 0.1 mm or less (mm) ０．１ : M ０．１ (3) The fiber reinforced resin molded product according to claim (1) or (2), characterized in that 1000 carbon fibers (A) randomly selected from the molded product have a fiber length distribution spread of 1.4 or more as shown in the following formula 3. Spread of fiber length distribution = (Σ(Li ２ ) / Σ(Li)) / (Σ(Li) / 1000) (Equation 3) Li: fiber length of each fiber (mm) Equation 3 can also be transformed into the following Equation 3-2: Spread of fiber length distribution=(Σ(Mi ２ ×Ni) / Σ(Mi×Ni)) / (Σ(Mi×Ni) / ΣNi) ... (Equation 3-2) Mi: length of each fiber (mm) Ni: number of fibers of Mi (4) The fiber reinforced plastic molded product according to any one of (1) to (3), characterized in that the carbon fiber (A) contains recycled carbon fiber. (5) The carbon fiber (A) contained in the fiber reinforced plastic molded product has a Raman shift of 1360 cm －１ The maximum Raman scattering intensity on the carbon fiber surface appears near I 1360 , Raman shift 1480 cm －１ Minimum Raman scattering intensity on the carbon fiber surface near I 1480 , Raman shift 1580 cm －１The maximum Raman scattering intensity on the carbon fiber surface appears near I 1580 The ratio of I 1360 / I 1580 and I 1480 / I 1580 The carbon fiber (A-2) has a different I compared to the carbon fiber (A-1). 1360 / I 1580 is larger or equal to I 1480 / I 1580(6) The fiber-reinforced resin molded product according to any one of (1) to (4), characterized in that the value of (A-1) is small. (7) The fiber-reinforced resin molded product according to (5), characterized in that, among the carbon fibers (A) contained in the fiber-reinforced resin molded product, the ratio of the number of carbon fibers (A-1) or (A-2) having a fiber length of 0.6 mm or more is 100:0 to 50:50. (8) The fiber-reinforced resin molded product according to (5) or (6), characterized in that the carbon fibers (A-2) are contained in an amount of 10 to 70 parts by weight per 100 parts by weight of the carbon fibers (A). (8) The ratio of the fiber diameter φ (A-1) of the carbon fiber (A-1) to the fiber diameter φ (A-2) of the carbon fiber (A-2), φ (A-1) / φ (A-2), is 1.2 or more and 2.0 or less (5) to (7). The fiber-reinforced resin molded product according to any one of (5) to (7), characterized in that (A-1) / φ (A-2) is 1.2 or more and 2.0 or less. (9) A fiber-reinforced resin molding material (C) containing carbon fiber (A) and thermoplastic resin (B), wherein the fiber length is 3 mm or more and 10 mm or less, and the carbon fiber (CF-1) and the thermoplastic resin (B) are oriented in the longitudinal direction of the molding material. A fiber-reinforced resin molding material (C-1) containing short fiber-shaped carbon fiber (CF-2) and a fiber-reinforced resin molding material (C-2) containing a thermoplastic resin (B), and the ratio of the fiber diameter φ (CF-1) of the carbon fiber (CF-1) to the fiber diameter φ (CF-2) of the carbon fiber (CF-2), φ (CF-1) / φ (CF-2) is 1.2 or more and 2.0 or less. (10) The fiber-reinforced resin molding material according to (9), wherein the carbon fibers (CF-2) are 1,000 carbon fibers (CF-2) randomly selected from the fiber-reinforced resin molding material (C-2), and the carbon fibers (CF-2) have a fiber length of 0.1 mm or more and 0.4 mm or less as shown in the following formula 4: Fiber length of carbon fiber (CF-2) = Σ(Li) / 1,000 (formula 4), Li: length of each fiber (mm), and formula 4 can be transformed into the following formula 4-2.Fiber length of carbon fiber (CF-2) = Σ (Mi × Ni) / ΣNi ... (Equation 4-2) Mi: length of each fiber (mm) Ni: number of fibers of Mi (11) The fiber reinforced resin molding material (C-1) according to (9) or (10), characterized in that it contains, in addition to the carbon fiber (CF-1) and the thermoplastic resin (B), a compound (D) different from the thermoplastic resin (B) present in a state filling the spaces between each fiber of the carbon fiber (CF-1). (12) The fiber reinforced resin molding material according to (9) to (11), characterized in that the carbon fiber (CF-2) contains recycled carbon fiber.

[0010] According to the present invention, it is possible to obtain a molded article that combines thin wall properties with complex shapes and mechanical properties. The molding material of the present invention has excellent flowability during molding processing, and can easily produce molded articles with excellent mechanical properties, so it can be applied not only to molding methods such as injection molding, transfer molding, blow molding, and insert molding, but also to a wide range of molding methods such as plunger molding, press molding, and stamping molding.

[0011] The molded articles of the present invention have excellent flowability during molding while maintaining excellent mechanical properties, and can be used for automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, and pedals; semiconductor and liquid crystal manufacturing equipment parts such as silicon wafer carriers, IC chip trays, electrolytic capacitor trays, and insulating films; industrial machinery parts such as compressor parts such as pumps, valves, and seals; and aircraft cabin interior parts; medical equipment parts such as sterilization instruments, columns, and piping; food and beverage manufacturing equipment parts; and electrical and electronic equipment parts and housings such as personal computers, office automation equipment, audiovisual equipment, mobile phones, telephones, home appliances, and toys. Using the molding material of the present invention, thin-walled molded articles of 0.5 to 2 mm can be obtained relatively easily, and the carbon fibers used as reinforcing fibers are conductive, which can impart electromagnetic wave shielding properties, making them suitable for electrical and electronic equipment parts and housings.

[0012] The present invention will be described in detail below with reference to embodiments.

[0013] <Molded Article> The molded article of the present invention contains carbon fibers (A) and a thermoplastic resin (B). By setting the long-to-short fiber length ratio of the carbon fibers (A) within a certain range, it is possible to contain a large amount of short carbon fibers while leaving long carbon fibers, thereby achieving both excellent mechanical properties and thin wall properties.

[0014] [Carbon Fiber (A)] The carbon fiber (A) of the present invention will be described. The type of carbon fiber (A) of the present invention is not particularly limited, and carbon fibers such as PAN (polyacrylonitrile), pitch, and rayon are preferably used. In particular, from the viewpoint of high strength, carbon fibers having a tensile strength of 3000 MPa or more are preferred, more preferably 4000 MPa or more. In terms of high modulus of elasticity, carbon fibers having a tensile modulus of 200 GPa or more are preferred, more preferably 300 GPa or more. In particular, carbon fibers having a modulus of elasticity of 300 GPa or more, which are difficult to maintain at a long fiber length, are preferred because they can better demonstrate the effects of the molding material of the present invention described below. The fiber diameter of the carbon fiber (A) is preferably 3 to 20 μm, more preferably 4 to 15 μm, and even more preferably 4.2 to 13 μm. If the fiber diameter is less than 3 μm, the number of intertwining points of the fibers in the molded article increases significantly, impairing the thinness and surface appearance of the molded article. In addition, recycled carbon fibers can be preferably used in combination from the viewpoints of the economic efficiency of the resulting molded product and the environmental impact.

[0015] It is preferable that a sizing agent is attached to the carbon fiber (A). By attaching the sizing agent to the carbon fiber (A), it is possible to improve the handleability during transport of the carbon fiber, the processability during the production of the molding material, and the mechanical properties and appearance properties of the molded product. There are no particular limitations on the type of sizing agent, but one or more types of sizing agents such as epoxy resins, urethane resins, acrylic resins, and various thermoplastic resins can be used in combination.

[0016] The amount of carbon fiber (A) is preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight, and even more preferably 10 to 30 parts by weight, relative to 100 parts by weight of the molded article. If the amount of carbon fiber (A) is less than 5 parts by weight, the mechanical properties may be insufficient, and if it exceeds 40 parts by weight, the carbon fiber (A) may be exposed on the surface of the molded article, resulting in a deterioration in the surface appearance.

[0017] The long-to-short fiber length ratio of the carbon fiber (A) in the molded article, as defined below, is 2 or more and 20 or less. It is more preferably 3 or more and 15 or less, and even more preferably 4 or more and 13 or less. When carbon fibers are used, fibers with a fiber length of 0.6 mm or more significantly affect the improvement of the impact strength of the molded article, but may be accompanied by a decrease in fluidity due to fiber interference during molding, which may cause a loss of thin-walledness of the molded article. Fibers with a fiber length of 0.1 mm or less are less likely to cause fiber interference during molding and can improve fluidity, thereby improving the thin-walledness of the molded article, but the improvement rates of strength and elastic modulus are significantly lower than those of fibers with a fiber length of 0.6 mm or more. Therefore, when the long-to-short fiber length ratio, which is related to the ratio of carbon fibers with a fiber length of 0.6 mm or more to carbon fibers with a fiber length of 0.1 mm or less, is less than 2, the mechanical properties may be insufficient, and when it exceeds 20, the carbon fiber (A) may be exposed on the surface of the molded article, resulting in a deterioration of the surface appearance.

[0018] Here, the "long-short fiber length ratio" in the present invention is the ratio of fibers having a fiber length of 0.6 mm or more to fibers having a fiber length of 0.1 mm or less, calculated by the following formula 1: Long-short fiber length ratio=Σ(L ０．６ ) / Σ(L ０．１ )...(Formula 1) L ０．６ : Length (mm) of fibers having a fiber length of 0.6 mm or more ０．１ : Length (mm) of fibers having a fiber length of 0.1 mm or less.

[0019] The long-short ratio of the fiber length can be measured by the following method. Using an optical microscope equipped with a hot stage, an appropriate test piece is cut out from the molded product, and the test piece is heated while sandwiched between glass plates on a hot stage appropriately set at 150 to 500°C, matching the melting temperature of the thermoplastic resin (B) used. The test piece is formed into a film, and the carbon fibers (A) are uniformly dispersed. The thermoplastic resin (B) is then observed in its molten state using an optical microscope (50 to 200 magnification). The fiber lengths of 1,000 randomly selected carbon fibers (A) are measured, and the long-short ratio is calculated using the above formula 1. Alternatively, a test piece cut out from the molded product is placed in a solvent that dissolves the thermoplastic resin (B), and appropriately heated to prepare a solution in which the carbon fibers (A) are uniformly dispersed. The solution is then filtered, and the carbon fibers (A) dispersed on the filter paper are observed using an optical microscope (50 to 200 magnification). The fiber lengths of 1,000 randomly selected carbon fibers (A) are measured, and the long-short ratio is calculated using the above formula 1. The filter paper used here may be quantitative filter paper (model number: No. 5C) manufactured by Advantec Co., Ltd.

[0020] The proportion of short fibers of carbon fiber (A) having a fiber length of 0.1 mm or less in the molded article is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. There is no particular restriction on the lower limit, and it may be 0%. If the proportion of short fibers exceeds 15%, the mechanical properties may be insufficient.

[0021] Here, the "short fiber ratio" in the present invention is the ratio of fibers having a length of 0.1 mm or less, calculated by the following formula 2: Short fiber ratio = Σ(L ０．１ ) / Σ(Li)×100(%)...(Formula 2) L ０．１ : Length (mm) of fibers having a fiber length of 0.1 mm or less Li: Fiber length (mm) of each fiber.

[0022] The proportion of short fibers is calculated by measuring the fiber lengths of 1,000 randomly selected carbon fibers (A) in the same manner as in the measurement of the long / short fiber length ratio, and then calculating the proportion of short fibers from the above formula 2.

[0023] The spread of the fiber length distribution of the carbon fiber (A) in the molded article is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. The upper limit is 30. If the spread of the fiber length distribution is less than 1.4, it may be difficult to achieve both mechanical properties and flowability.

[0024] Here, the "spread of fiber length distribution" in the present invention is a value calculated from the following formula 3: Spread of fiber length distribution = (Σ(Li ２ ) / Σ(Li)) / (Σ(Li) / 1000) (Equation 3) Li: fiber length of each fiber (mm).

[0025] The spread of the fiber length distribution is calculated by measuring the fiber lengths of 1,000 randomly selected carbon fibers (A) in the same manner as in the measurement of the long / short fiber length ratio, and then calculating the spread of the fiber length distribution from the above formula 3.

[0026] The carbon fiber (A) contained in the molded article of the present invention preferably contains recycled carbon fiber. Here, the recycled carbon fiber refers to carbon fiber recovered and reused from a molded article containing used carbon fiber, or from a resin composition containing carbon fiber or process waste of a molded article.

[0027] The carbon fiber (A) in the molded article may contain two or more types of carbon fiber having different properties such as different strength, modulus of elasticity, fiber diameter, surface condition, and fiber length depending on the purpose. Three or more types of carbon fiber may be contained, but in the molded article of the present invention, it is preferable that the carbon fiber (A) contains two types of carbon fiber (A-1) and carbon fiber (A-2) having different properties, and that the carbon fiber (A-1) has a fiber length of 0.6 mm or more. It is also preferable that the carbon fiber (A-2) is a material having a shorter fiber length than the carbon fiber (A-1), which can improve the filling ability into details and the thin wall thickness while maintaining the mechanical properties of the resulting molded article.

[0028] Methods for distinguishing between carbon fiber (A-1) and carbon fiber (A-2) include known techniques for analyzing carbon fibers, such as optical microscope observation, scanning electron microscope observation, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. In the present invention, carbon fiber (A-1) and carbon fiber (A-2) can be distinguished from each other by a laser Raman spectrometer, using a Raman spectrum obtained at a Raman shift of 1360 cm －１ The maximum Raman scattering intensity on the carbon fiber surface appears near I 1360 , Raman shift 1480 cm －１ Minimum Raman scattering intensity on the carbon fiber surface near I 1480 , Raman shift 1580 cm －１ The maximum Raman scattering intensity on the carbon fiber surface appears near I 1580 The ratio of I 1360 / I 1580 and I 1480 / I 1580 The carbon fiber (A-2) has a higher I than the carbon fiber (A-1). 1360 / I 1580 is larger or equal to I 1480 / I 1580 is defined as a carbon fiber having a small value.

[0029] In the carbon fibers (A) in the molded article of the present invention, the ratio A-1:A-2 of the number of carbon fibers (A-1) to the number of carbon fibers (A-2) is preferably 100:0 to 50:50, more preferably 100:0 to 80:20, and even more preferably 100:0. A larger difference between the ratio of the number of carbon fibers (A-1) to the number of carbon fibers (A-2) having a fiber length of 0.6 mm or more is preferred, as this improves the fluidity during molding and facilitates improved filling of fine details while maintaining the mechanical properties of the molded article.

[0030] From the viewpoint of reducing waste, it is preferable to use recycled carbon fiber for the carbon fiber (A-2) out of the carbon fiber (A-1) and the carbon fiber (A-2). Fibers produced by known manufacturing methods can be used as recycled carbon fibers. For example, a method of obtaining recycled carbon fiber by performing the following steps (a) to (c) can be mentioned. (a) A crushing step in which fiber-reinforced resin waste is crushed to produce crushed pieces having a predetermined fiber length. (b) A pyrolysis treatment step in which the crushed pieces are heated while being supplied in a fixed amount to a pyrolysis furnace, and the matrix resin component is removed to obtain a pyrolyzed product. (c) A classification step in which the pyrolyzed product is classified by fiber length to obtain recycled carbon fiber. A sizing agent may be applied to the recycled carbon fiber after the classification step.

[0031] The recycled carbon fiber is preferably contained in an amount of 10 to 70 parts by weight, more preferably 20 to 70 parts by weight, per 100 parts by weight of the carbon fiber (A). If the amount is less than 10 parts by weight, the filling of fine details may be insufficient, and if the amount is more than 70 parts by weight, the mechanical properties may be insufficient.

[0032] The two types of carbon fibers (A-1) and (A-2) contained in the carbon fiber (A) preferably have different fiber diameters. The carbon fiber (A-1) preferably has a larger diameter than the carbon fiber (A-2), and the ratio of the fiber diameter φ(A-1) of the carbon fiber (A-1) to the fiber diameter φ(A-2) of the carbon fiber (A-2), φ(A-1) / φ(A-2), is more preferably 1.2 or more and 2.0 or less. It is even more preferably 1.3 or more and 1.8 or less. By setting the ratio within the above range, it becomes easier to maintain the filling ability of the fine details while retaining the fiber length in the molded article.

[0033] The carbon fiber (A-2) may be in a monofilament dispersed state or may partially contain bundled fibers. The inclusion of bundled fibers increases the impact strength of a molded article compared to a monofilament dispersed state, but the bundled fibers may protrude from the surface of the molded article. A monofilament dispersed state is preferred, which results in a slightly lower impact strength compared to a monofilament dispersed state, but excellent appearance and mechanical properties of the molded article.

[0034] Preferably, the carbon fiber (A-1) is derived from (CF-1) contained in the molding material (C-1) described later, and the carbon fiber (A-2) is derived from (CF-2) contained in the molding material (C-2) described later.

[0035] [Thermoplastic Resin (B)] The molded article of the present invention contains 60 to 95 parts by weight of thermoplastic resin (B) per 100 parts by weight of the total of carbon fiber (A) and thermoplastic resin (B).

[0036] 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, and two or more of these can also be used. Among the thermoplastic resins, polyolefin resins, polyamide resins, polycarbonate resins, and polyarylene sulfide resins are more preferred because they are lightweight and have an excellent balance of mechanical properties and moldability.

[0037] 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 and at least one α-olefin, conjugated diene, non-conjugated diene, or the like. Examples of α-olefins copolymerized with propylene 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 and non-conjugated dienes copolymerized with propylene include butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Two or more of these may be used. Examples of the skeletal structure of the 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.

[0038] Furthermore, 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 bound 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. 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. Furthermore, compounds having unsaturated vinyl groups other than olefins may also be used.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] Two or more of these may be used. Among these, ethylenically unsaturated carboxylic acid anhydrides are preferred, with maleic anhydride being more preferred.

[0043] 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.

[0044] 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.

[0045] In the present invention, polyamide resins having a melting point of 170° 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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).

[0053] 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

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] <Molding Material> The fiber-reinforced resin molding of the present invention can be produced, for example, by molding using the molding material described below by a known method. The fiber-reinforced resin molding material of the present invention contains carbon fibers (A) and a thermoplastic resin (B). By containing carbon fibers (A), the fiber length of the carbon fibers can be maintained while maintaining fluidity, and a molded article exhibiting excellent mechanical properties can be obtained.

[0060] The fiber-reinforced resin molding material of the present invention contains carbon fibers (A) and a thermoplastic resin (B). The type of thermoplastic resin (B) is not particularly limited, and examples thereof include the thermoplastic resins described in the description of the thermoplastic resin (B) of the molded article. The types of preferred thermoplastic resins and the reasons for their preference are also the same.

[0061] The fiber-reinforced resin molded article of the present invention has a fiber length of 3 mm to 10 mm and is oriented in the longitudinal direction of the molding material. The fiber-reinforced resin molding material (C-1) and the short fiber-like carbon fiber (CF-2) and the thermoplastic resin (B) are included. The fiber-reinforced resin molding material (C-2) containing the short fiber pellets are preferably dry-blended and subjected to molding. The carbon fiber (A-1) derived from the carbon fiber (CF-1) contained in the molding material (C-1) and the carbon fiber (A-2) derived from the carbon fiber (CF-2) contained in the molding material (C-2) can be easily adjusted. Here, dry blending differs from blending that involves melt kneading in that it refers to stirring and mixing multiple materials at a temperature at which the resin components do not melt, to produce a substantially homogeneous state, and is preferably used when using pellet-shaped molding materials, such as in injection molding or extrusion molding.

[0062] The carbon fiber (CF-1) contained in the molding material (C-1) and the carbon fiber (CF-2) contained in the molding material (C-2) preferably have different fiber diameters, with the carbon fiber (CF-1) having a larger diameter than the carbon fiber (CF-2). The ratio of the fiber diameter φ(CF-1) of the carbon fiber (CF-1) to the fiber diameter φ(CF-2) of the carbon fiber (CF-2), φ(CF-1) / φ(CF-2), is preferably 1.2 or more and 2.0 or less. It is more preferably 1.3 or more and 1.8 or less. By setting the ratio within the above range, breakage of the carbon fiber (CF-1) during molding can be suppressed, and the long / short fiber length ratio, short fiber proportion, and fiber length distribution in the molded product can be appropriately controlled, which is preferable. By suppressing breakage of the carbon fiber (CF-1) to fibers with a fiber length of less than 0.1 mm, high mechanical properties can be exhibited even with a small amount of carbon fiber (CF-1) content.

[0063] <Molding Material (C-1)> The type of carbon fiber (CF-1) contained in the fiber-reinforced resin molding material (C-1) containing carbon fiber (CF-1) having a fiber length of 3 mm or more and 10 mm or less and oriented in the longitudinal direction of the molding material and a thermoplastic resin (B) is not particularly limited, and examples thereof include the carbon fibers described in the description of the carbon fiber (A) of the molded product. The length of the carbon fiber (CF-1) is 3 to 10 mm, preferably 5 to 9 mm. The carbon fiber (CF-1) is preferably in a state in which the monofilaments are arranged in one direction. Preferred forms include unidirectional fiber bundles, bidirectional fiber bundles, and multidirectional fiber bundles, but from the viewpoint of productivity in the process of producing the molding material, unidirectional fiber bundles are more preferably used. The carbon fiber (CF-1) with a higher number of monofilaments is more economically advantageous; therefore, when the molding material is formed into pellets, for example, the number of monofilaments in one pellet is preferably 10,000 or more. On the other hand, since the greater the number of single filaments of the carbon fiber, the more disadvantageous it tends to be for impregnation with the matrix resin. From the viewpoint of achieving both economical efficiency and impregnation performance, a number of 15,000 to 100,000 is more preferable, and a number of 20,000 to 50,000 is particularly preferable. Furthermore, it is preferable that the carbon fiber (CF-1) in the molding material is aligned in the longitudinal direction of the molding material, and that the length of the carbon fiber (CF-1) is substantially the same as the length of the molding material. Here, "aligned in the longitudinal direction of the molding material" refers to a state in which the long axis of the carbon fiber (CF-1) and the long axis of the molding material are oriented in the same direction, and the angular deviation 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, for example, in a pellet-shaped molding material, the carbon fiber (CF-1) is not cut midway inside the pellet, and carbon fiber (CF-1) significantly shorter than the full length of the pellet is not substantially contained. The full length of the pellet is the length in the orientation direction of the carbon fiber (CF-1) in the pellet. By having the carbon fiber (CF-1) have substantially the same length as the molding material, the carbon fiber length in the molded product can be increased, and excellent mechanical properties and dimensional accuracy can be obtained.

[0064] The fiber-reinforced resin molding material (C-1) of the present invention preferably contains, in addition to the carbon fiber (CF-1) and the thermoplastic resin (B), a compound (D) different from the thermoplastic resin (B) that is present in a state of filling the spaces between the carbon fiber (CF-1). The presence of compound D in a state of filling the spaces between the fibers can improve the dispersion of the fibers during molding and can also suppress fiber breakage during molding.

[0065] The compound (D) preferably has a lower melt viscosity than the thermoplastic resin (B). Because the melt viscosity of the compound (D) is lower than that of the thermoplastic resin (B), the fluidity of the compound (D) is high when molding the molding material, which can further improve the dispersion effect of the carbon fiber (CF-1) in the thermoplastic resin (B), and can suppress fiber breakage. Furthermore, the compound (D) preferably has a high affinity with the thermoplastic resin (B). By selecting an impregnating resin that has a high affinity with the thermoplastic resin (B), it is efficiently compatible with the thermoplastic resin (B) during molding, thereby further improving the dispersibility of the carbon fiber.

[0066] The compound (D) is preferably a resin selected from the group consisting of epoxy resins, phenolic resins, and terpene resins, and examples thereof include homopolymers and reaction products with other components. By pre-impregnating the carbon fiber (CF-1) with the compound (D), dispersibility can be efficiently improved during molding, and thus the compound (D) is preferably used.

[0067] The number average molecular weight of compound (D) is preferably 200 to 5,000. If the number average molecular weight is 200 or more, the bending strength and tensile strength of the molded article can be further improved. The number average molecular weight is more preferably 1,000 or more. Furthermore, if the number average molecular weight is 5,000 or less, the viscosity of the compound is appropriately low, so that the impregnation ability into carbon fiber (A-1) is excellent and the dispersibility of carbon fiber in the molded article can be further improved. The number average molecular weight is more preferably 3,000 or less. The number average molecular weight of such a compound can be measured using gel permeation chromatography (GPC).

[0068] The amount of compound (D) is preferably 0.1 to 20 parts by weight, more preferably 3 to 10 parts by weight, per 100 parts by weight of molding material (C-1). By adjusting the amount within this range, a molding material with excellent moldability and handleability can be obtained.

[0069] <Molding material (C-2)> The type of carbon fiber (CF-2) contained in the fiber-reinforced resin molding material (C-2) containing short fiber-like carbon fiber (CF-2) and thermoplastic resin (B) is not particularly limited, and examples thereof include the carbon fibers described in the description of the carbon fiber (A) of the molded product.

[0070] The molding material (C-2) is obtained by melt-kneading the thermoplastic resin (B) and carbon fiber. The form of the carbon fiber raw material used during melt-kneading is not particularly limited as long as it can be fed into a melt-kneading device, and examples include pre-cut chopped strands, crushed fibers, continuous long fibers, etc., with chopped strands being preferred from the viewpoint of productivity. The chopped strands may be recycled chopped strands obtained by pulverizing a fiber-reinforced resin molded product and pyrolyzing the matrix resin. The recycled chopped strands can be obtained by a known manufacturing method.

[0071] The fiber length of the carbon fiber (CF-2) contained in the molding material (C-2) is preferably 0.1 to 0.4 mm, more preferably 0.2 to 0.4 mm. If the fiber length of the carbon fiber (CF-2) is less than 0.1 mm, the mechanical properties of the molded article may be insufficient. On the other hand, if the fiber length of the carbon fiber (CF-2) is 0.4 mm or more, the flowability during molding may be insufficient.

[0072] Here, the "fiber length of carbon fiber (CF-2)" contained in molding material (C-2) in the present invention refers to the number average fiber length calculated from the following formula 4: Fiber length of carbon fiber (CF-2) = Σ(Li) / 1000 (formula 4), where Li is the length of each fiber (mm).

[0073] The fiber length of the carbon fiber (CF-2) can be measured by the method described in the method for measuring the fiber length of the carbon fiber contained in the molded article. The fiber lengths of 1,000 randomly selected carbon fibers (CF-2) are measured, and the fiber length is calculated using the above formula 4.

[0074] The fiber-reinforced resin molding material of the present invention may also contain recycled carbon fibers, as in the above-described molded product, and it is preferable that the carbon fibers (CF-2) contain recycled carbon fibers.

[0075] 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 the various properties used in these examples will be described.

[0076] (1) Fiber length ratio of carbon fiber (A) in molded article A test piece cut out from a molded article was placed in a solvent that dissolves the thermoplastic resin (B) used in each example and comparative example, and was appropriately heated to obtain a solution in which the carbon fiber (A) was uniformly dispersed. The solution was then filtered using quantitative filter paper (No. 5C) manufactured by Advantec Co., Ltd., and the carbon fiber (A) dispersed on the filter paper was observed under an optical microscope (50 to 200 magnifications). The fiber lengths of 1,000 randomly selected carbon fibers (A) were measured, and the fiber length ratio, expressed as the ratio of fibers with a length of 0.6 mm or more to fibers with a length of 0.1 mm or more, was calculated using the following formula 1. Fiber length ratio = Σ(L ０．６ ) / Σ(L ０．１ ) ... (Formula 1) L ０．６ : Length (mm) of fibers having a fiber length of 0.6 mm or more ０．１ : Length (mm) of fibers having a fiber length of 0.1 mm or less.

[0077] (2) Short Fiber Proportion of Carbon Fiber (A) in Molded Article Carbon fiber (A) was observed under an optical microscope (50 to 200 magnifications) in the same manner as in (1) above. The fiber lengths of 1,000 randomly selected carbon fibers (A) were measured, and the short fiber proportion, expressed as the proportion of fibers with a length of 0.1 mm or less, was calculated using the following formula 2: Short fiber proportion = Σ(L ０．１ ) / Σ(Li)×100(%) ...(Formula 2) L ０．１: Length (mm) of fibers having a fiber length of 0.1 mm or less Li: Fiber length (mm) of each fiber.

[0078] (3) Spread of fiber length distribution of carbon fiber (A) in molded product Carbon fiber (A) was observed under an optical microscope (50 to 200 magnifications) in the same manner as in (1) above. The fiber lengths of 1,000 randomly selected carbon fibers (A) were measured, and the spread of fiber length distribution was calculated using the following formula 3. Spread of fiber length distribution = (Σ(Li ２ ) / Σ(Li)) / (ΣLi / 1000) (Equation 3) Li: fiber length of each fiber (mm).

[0079] (4) The ratio of the number of carbon fibers (A-1) and (A-2) having a fiber length of 0.6 mm or more in the molded product. The carbon fibers (A) were observed under an optical microscope (50 to 200 magnifications) in the same manner as in (1) above. The fiber lengths of 400 randomly selected carbon fibers (A) were measured, and fibers having a fiber length of 0.6 mm or more were extracted. Each of the extracted fibers was measured using a laser Raman spectrophotometer, and the Raman shift of the obtained Raman spectrum was 1360 cm. －１ The maximum Raman scattering intensity on the carbon fiber surface appears near the Raman shift of 1480 cm －１ The minimum Raman scattering intensity on the carbon fiber surface appears near the Raman shift of 1580 cm －１ The carbon fiber (A-1) and the carbon fiber (A-2) were identified based on the ratio of the maximum value of Raman scattering intensity on the carbon fiber surface appearing near the maximum value, and the ratio of the number of fibers having a fiber length of 0.6 mm or more in the carbon fiber (A-1) and the carbon fiber (A-2) was calculated.

[0080] (5) 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 The calculated values ​​were evaluated according to the following criteria, with A and B being considered acceptable. A: 11 KJ / m ２ More than B:9KJ / m ２ More than 11KJ / m ２ Less than C: 9KJ / m２ less than.

[0081] (6) Measurement of flexural strength and flexural modulus of molded products Flexural properties were measured for ISO dumbbell test pieces obtained by injection molding the molding material according to ISO 178 (1993). A three-point bending test jig (indenter radius 5 mm) was used, with a support distance of 64 mm, and the flexural modulus was measured at a test speed of 2 mm / min. The test machine used was an "Instron (registered trademark)" universal testing machine, model 5566 (manufactured by Instron Corporation). Evaluation was performed according to the following criteria, with A and B being considered acceptable. Flexural strength: A: 410 MPa or more; B: 380 MPa or more, less than 410 MPa; C: 330 MPa or more, less than 380 MPa; D: 260 MPa or more, less than 330 MPa; E: less than 260 MPa. Flexural modulus A: 22 GPa or more B: 21 GPa or more but less than 22 GPa C: 17 MPa or more but less than 21 GPa D: less than 17 MPa.

[0082] (7) Measurement of tensile strength of molded product The flexural properties of ISO type dumbbell test pieces obtained by injection molding the molding material were measured according to ISO 527 (1993). The flexural modulus was measured using a tensile test jig with a grip distance of 115 mm and a test speed of 5 mm / min. The test machine used was an "Instron (registered trademark)" universal testing machine, Model 5566 (manufactured by Instron Corporation). Evaluation was made according to the following criteria, with A and B being considered pass. A: 260 MPa or more B: 240 MPa or more but less than 260 MPa C: 200 MPa or more but less than 240 MPa D: 160 MPa or more but less than 200 MPa E: Less than 160 MPa

[0083] (8) Fiber length in molding material (C-2) A test piece extracted from molding material (C-2) was 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 carbon fiber (A) was uniformly dispersed. The solution was then filtered using Advantec quantitative filter paper (No. 5C), and the carbon fiber (CF-2) dispersed on the filter paper was observed under an optical microscope (50 to 200 magnifications). The fiber lengths of 1,000 randomly selected carbon fibers (A) were measured and calculated using the following formula 4. Fiber length of carbon fiber (CF-2) = Σ(Li) / 1,000 (Formula 4) Li: length of each fiber (mm).

[0084] (9) Fluidity of Molding Material The molding material was injection molded in an injection molding machine using a mold with a width of 10 mm, a length of 125 mm, and a thickness of 2 mm under the following conditions: an injection speed of 30 mm / s, a back pressure of 10 MPa, a holding pressure of 40 MPa, a cylinder temperature of 260°C, and a mold temperature of 80°C. The cylinder peak pressure when producing a molded product was used as an index of fluidity. The cylinder pressure was the average value of 20 shots, and this average value was used for evaluation of each example and comparative example. Evaluation was made according to the following criteria, with A and B being considered acceptable. A: less than 90 MPa B: 90 MPa or more but less than 110 MPa C: 110 MPa or more

[0085] Reference Example 1 Preparation of Carbon Fiber (CF-1) For carbon fiber "TORAYCA" (registered trademark) T700S-24000 manufactured by Toray Industries, Inc. (total number of single fibers: 24,000, single fiber diameter: 7 μm), a sizing agent mother solution was prepared by dissolving glycerol polyglycidyl ether as a polyfunctional compound in water to a concentration of 2% by weight, and the sizing agent was applied to the carbon fiber by a dipping method, followed by drying at 230° C. The amount of sizing agent attached to the carbon fiber thus obtained was 1.0% by weight.

[0086] Reference Example 2 Preparation of Carbon Fiber (CF-2)-(1) Carbon fiber "TORAYCA" (registered trademark) manufactured by Toray Industries, Inc. T700S-24000 (total number of single fibers 24,000, single fiber diameter 7 μm) was used. A sizing agent mother solution was prepared by dissolving glycerol polyglycidyl ether as a polyfunctional compound in water to a concentration of 2% by weight, and the sizing agent was applied to the carbon fiber by an immersion method, followed by drying at 230 ° C. The amount of sizing agent attached to the obtained carbon fiber was 1.0% by weight. The carbon fiber thus obtained was cut with a cartridge cutter to obtain carbon fiber chopped yarns with a chopped length of 6 mm.

[0087] Reference Example 3 Preparation of Carbon Fiber (CF-2)-(2) Carbon fiber "TORAYCA" (registered trademark) Toray Industries, Inc. prepreg P3252S-12 (single fiber diameter 7 μm) was used. A carbon fiber reinforced plastic (CFRP) molded product was prepared by applying a pressure of 0.6 MPa in a press and heating at 160 ° C for 2 hours. The resulting CFRP was crushed and classified to obtain waste CFRP pieces. The waste CFRP pieces were uniformly spread in a metal tub and placed in an electric muffle furnace with an internal volume of 59 liters. While introducing nitrogen gas into the furnace, the treatment temperature was maintained at 500 ° C. and heat-treated for 3.5 hours. Thereafter, similarly, while introducing air into the furnace, the treatment temperature was maintained at a predetermined temperature (300 ° C.) and heat-treated for 2 hours to obtain recycled carbon fiber chopped yarn.

[0088] Reference Example 4 Preparation of Carbon Fiber (CF-2)-(3) Carbon fiber "TORAYCA" (registered trademark) Toray Industries, Inc. prepreg P2252S-12 (single fiber diameter 5 μm) was used. A carbon fiber reinforced plastic (CFRP) molded product was prepared by applying a pressure of 0.6 MPa in a press and heating at 160 ° C for 2 hours. The resulting CFRP was crushed and classified to obtain waste CFRP pieces. The waste CFRP pieces were spread evenly in a metal tub and placed in an electric muffle furnace with an internal volume of 59 liters. While introducing nitrogen gas into the furnace, the treatment temperature was maintained at 500 ° C. and heat-treated for 3.5 hours. Thereafter, similarly, while introducing air into the furnace, the treatment temperature was maintained at a predetermined temperature (300 ° C.) and heat-treated for 2 hours to obtain recycled carbon fiber chopped yarn.

[0089] Reference Example 5 Preparation of Carbon Fiber (CF-2)-(4) Carbon fiber "TORAYCA" (registered trademark) Toray Industries, Inc. prepreg P2252S-12 (single fiber diameter 5 μm) was used. A carbon fiber reinforced plastic (CFRP) molded product was produced by applying a pressure of 0.6 MPa in a press and heating at 160 ° C for 2 hours. The resulting CFRP was crushed and classified to obtain waste CFRP pieces. The waste CFRP pieces were uniformly spread in a metal tub and placed in an electric muffle furnace with an internal volume of 59 liters. While introducing nitrogen gas into the furnace, the treatment temperature was maintained at 400 ° C. and heat-treated for 1 hour. Thereafter, similarly, while introducing air into the furnace, the treatment temperature was maintained at a predetermined temperature (300 ° C.) and heat-treated for 1 hour to obtain recycled carbon fiber chopped yarn. The resulting recycled carbon fiber chopped yarn had some fibers bound together by the residual resin of the CFRP to form bundles.

[0090] <Thermoplastic resin (B)> (B-1) Polyamide 6 resin (Nylon 6 resin "Amilan" (registered trademark) CM1001 manufactured by Toray Industries, Inc.) (B-2) Polycarbonate resin ("Iupilon" (registered trademark) S-3000 manufactured by Mitsubishi Engineering Plastics Corporation) (B-3) Polypropylene resin ("Prime Polypro" (registered trademark) J137G manufactured by Prime Polymer Co., Ltd.) / Maleic acid-modified polypropylene resin ("Admer" (registered trademark) QE840 manufactured by Mitsui Chemicals, Inc.) blended in a weight ratio of 90 / 10) was used.

[0091] <Compound (D)> (D-1) Terpene phenol resin (YS Polystar N125, manufactured by Yasuhara Chemical Co., Ltd.) (D-2) Bisphenol A epoxy resin (jER (registered trademark) 1004AF, manufactured by Mitsubishi Chemical Corporation) (D-3) Hydrogenated terpene resin (CLEARON (registered trademark) P125, manufactured by Yasuhara Chemical Co., Ltd.) were used.

[0092] Example 1 A long fiber reinforced resin pellet manufacturing apparatus was used, equipped with a coating die for a wire resin coating method 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. The extruder cylinder temperature was set to 230°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 compound (D-1) heated and melted at 250°C was discharged in an amount of 6 parts by weight per 100 parts by weight of the total of the carbon fiber (CF-1) and the thermoplastic resin (B-1). Thereafter, the compound (D-1) was discharged and impregnated into a fiber bundle made of carbon fiber (CF-1), and then the fiber bundle of carbon fiber (CF-1) to which the compound (D-1) was applied was supplied to a die hole (diameter 3 mm) through which the molten thermoplastic resin (B-1) was discharged, and the fiber bundle of carbon fiber (CF-1) was continuously arranged so that the thermoplastic resin (B) covered the periphery of the carbon fiber (CF-1). At this time, the internal cross section of the fiber bundle was such that at least a portion of the carbon fiber (CF-1) was in contact with the thermoplastic resin (B-1). After cooling the obtained strand, it was cut into pellets 7 mm long with a cutter to obtain a fiber-reinforced resin molding material (C-1)-(1). At this time, the take-up speed was adjusted so that the carbon fiber (CF-1) was 30 parts by weight relative to a total of 100 parts by weight of (CF-1) and (B-1). The length of the carbon fiber (CF-1) in the obtained fiber-reinforced resin molding material (C-1)-(1) was substantially the same as the pellet length, and the carbon fiber bundles were aligned parallel to the axial direction of the molding material.

[0093] Next, after feeding the thermoplastic resin (B-1) into the main hopper of another twin-screw extruder (TEX30α manufactured by The Japan Steel Works, Ltd.), carbon fiber (CF-2)-(1) was fed into the molten resin from the side feeder, and the screw rotation speed was set to 200 rpm. The strand discharged from the die was cooled in water, cut to a length of 3.0 mm with a strand cutter, and pelletized to obtain a fiber-reinforced resin molding material (C-2)-(1). At this time, the amount of carbon fiber (CF-2)-(1) added was adjusted so that the total weight of the carbon fiber (CF-2)-(1) was 30 parts by weight, relative to 100 parts by weight of the total of (CF-2)-(1) and (B-1).

[0094] The fiber reinforced resin molding materials (C-1)-(1) and (C-2)-(1) thus obtained were dry blended in the proportions shown in Table 1 to obtain a fiber reinforced resin molding material (C) as an intermediate raw material. The fiber reinforced resin molding material (C) thus obtained was injection molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd. J110AD) under the following conditions: injection speed: 30 mm / s, back pressure: 10 MPa, dwell pressure: 40 MPa, dwell time: 10 seconds, cylinder temperature: 260 ° C., mold temperature: 80 ° C., and an ISO dumbbell test piece was prepared as a molded product. The cylinder peak pressure during molding was measured. The carbon fiber (CF-1), carbon fiber (CF-2), thermoplastic resin (B-1), and compound (D) composition ratios in Table 1 were adjusted by the dry blend ratio. 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 a 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 a relative humidity of 50%, and then subjected to characteristic evaluation. The evaluation results obtained by the above-mentioned methods are summarized in Table 1.

[0095] Examples 2 to 11, Comparative Examples 1 to 6 Materials and molded articles were obtained in the same manner as in Example 1 above, except that the ratios of the components were as shown in Tables 1 to 3.

[0096] Example 12 A long fiber reinforced resin pellet manufacturing apparatus was used, equipped with a coating die for a wire resin coating method 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. The extruder cylinder temperature was set to 300 ° C., and the thermoplastic resin (B-2) described above was fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The compound (D-2) heated and melted at 250 ° C. was discharged in an amount of 6 parts by weight per 100 parts by weight of the total of the carbon fiber (CF-1) and the thermoplastic resin (B-2). The amount of the compound (D-2) was adjusted. Thereafter, the compound (D-2) was discharged and impregnated into a fiber bundle made of carbon fiber (CF-1), and then the fiber bundle of carbon fiber (CF-1) to which the compound (D-2) was applied was supplied to a die hole (diameter 3 mm) through which the molten thermoplastic resin (B-2) was discharged, and the fiber bundle of carbon fiber (CF-1) was continuously arranged so that the thermoplastic resin (B-2) covered the periphery of the carbon fiber (CF-1). At this time, the internal cross section of the fiber bundle was such that at least a portion of the carbon fiber (CF-1) was in contact with the thermoplastic resin (B-2). After cooling the obtained strand, it was cut into pellets 7 mm long with a cutter to obtain a fiber-reinforced resin molding material (C-1)-(2). At this time, the take-up speed was adjusted so that the carbon fiber (CF-1) was 30 parts by weight relative to a total of 100 parts by weight of (CF-1) and (B-2). The length of the carbon fiber (CF-1) in the obtained fiber reinforced resin molding material (C-1)-(2) was substantially the same as the pellet length, and the carbon fiber bundles were aligned parallel to the axial direction of the molding material.

[0097] Next, after feeding the thermoplastic resin (B-2) into the main hopper of another twin-screw extruder (TEX30α manufactured by The Japan Steel Works, Ltd.), carbon fiber (CF-2)-(3) was fed into the molten resin from the side feeder, and the screw rotation speed was set to 200 rpm. The strand discharged from the die was cooled in water, cut to a length of 3.0 mm with a strand cutter, and pelletized to obtain a fiber-reinforced resin molding material (C-2)-(2). At this time, the amount of carbon fiber (CF-2)-(3) added was adjusted so that the carbon fiber (CF-2)-(3) was 30 parts by weight relative to a total of 100 parts by weight of (CF-2)-(3) and (B-2).

[0098] The fiber reinforced resin molding material (C) thus obtained was dry blended in the proportions shown in Table 4 to obtain the intermediate fiber reinforced resin molding material (C). The fiber reinforced resin molding material (C) thus obtained was injection molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd., J110AD) under the following conditions: injection speed: 30 mm / s, back pressure: 10 MPa, dwell pressure: 40 MPa, dwell time: 10 seconds, cylinder temperature: 300 ° C., mold temperature: 80 ° C., and the ISO dumbbell test piece was prepared as a molded product. The cylinder peak pressure during molding was measured. The carbon fiber (CF-1), carbon fiber (CF-2), thermoplastic resin (B), and compound (D) composition ratios in Table 4 were adjusted by the dry blend ratio. 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 a 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 a relative humidity of 50%, and then subjected to evaluation of the properties. The evaluation results obtained by the above-mentioned methods are summarized in Table 4.

[0099] Comparative Example 7 A material and a molded article were obtained in the same manner as in Example 12 above, except that the ratios of the components were as shown in Table 4.

[0100] Example 13 A long fiber reinforced resin pellet manufacturing apparatus was used, equipped with a coating die for a wire resin coating method 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. The extruder cylinder temperature was set to 220 ° C., and the thermoplastic resin (B-3) described above was fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm. The compound (D-3) heated and melted at 200 ° C. was discharged in an amount of 6 parts by weight per 100 parts by weight of the total of the carbon fiber (CF-1) and the thermoplastic resin (B-3). Thereafter, the compound (D-3) was discharged and impregnated into a fiber bundle made of carbon fiber (CF-1), and then the fiber bundle of carbon fiber (CF-1) to which the compound (D-3) was applied was supplied to a die hole (diameter 3 mm) through which the molten thermoplastic resin (B-3) was discharged, and the fiber bundle of carbon fiber (CF-1) to which the compound (D-3) was applied was continuously arranged so that the thermoplastic resin (B-3) covered the periphery of the carbon fiber (CF-1). At this time, the internal cross section of the fiber bundle was such that at least a portion of the carbon fiber (CF-1) was in contact with the thermoplastic resin (B-3). After cooling the obtained strand, it was cut into pellets 7 mm long with a cutter to obtain a fiber-reinforced resin molding material (C-1)-(3). At this time, the take-up speed was adjusted so that the carbon fiber (CF-1) was 30 parts by weight relative to a total of 100 parts by weight of (CF-1) and (B-3). The length of the carbon fiber (CF-1) in the obtained fiber reinforced resin molding material (C-1)-(3) was substantially the same as the pellet length, and the carbon fiber bundles were aligned parallel to the axial direction of the molding material.

[0101] Next, after feeding the thermoplastic resin (B-3) into the main hopper of another twin-screw extruder (TEX30α manufactured by The Japan Steel Works, Ltd.), carbon fiber (CF-2)-(3) was fed into the molten resin from the side feeder, and the screw rotation speed was set to 200 rpm. The strand discharged from the die was cooled in water, cut to a length of 3.0 mm with a strand cutter, and pelletized to obtain a fiber-reinforced resin molding material (C-2)-(3). At this time, the amount of carbon fiber (CF-2)-(3) added was adjusted so that the total weight of the carbon fiber (CF-2)-(3) was 30 parts by weight, relative to a total of 100 parts by weight of (CF-2)-(3) and (B-3).

[0102] The fiber reinforced resin molding material (C) thus obtained was dry blended in the proportions shown in Table 4 to obtain the intermediate fiber reinforced resin molding material (C). The fiber reinforced resin molding material (C) thus obtained was injection molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd., J110AD) under the following conditions: injection speed: 30 mm / s, back pressure: 10 MPa, dwell pressure: 40 MPa, dwell time: 10 seconds, cylinder temperature: 230 ° C., mold temperature: 60 ° C., and the ISO type dumbbell test piece as a molded product was prepared. The cylinder peak pressure during molding was measured. The carbon fiber (A-1), carbon fiber (A-2), thermoplastic resin (B), and compound (D) composition ratios in Table 1 were adjusted by the dry blend ratio. 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 a 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 a relative humidity of 50%, and then subjected to evaluation of the properties. The evaluation results obtained by the above-mentioned methods are summarized in Table 4.

[0103] Comparative Example 8 A material and a molded article were obtained in the same manner as in Example 13 above, except that the ratios of the components were as shown in Table 4.

[0104]

[0105]

[0106]

[0107]

[0108] Examples 1 and 2 showed excellent mechanical properties and fluidity, but Example 3, due to the use of recycled chopped carbon fiber, showed slightly inferior mechanical properties compared to Example 2, but still showed excellent mechanical properties. Examples 4 to 7 also showed excellent mechanical properties and fluidity even when the fiber type was changed, and showed similar mechanical properties even when the amount of recycled chopped carbon fiber yarn was increased compared to Examples 1 to 3. Examples 8 to 11 showed excellent mechanical properties and fluidity, although slightly inferior compared to Examples 4 to 7. Examples 12 and 13 showed excellent mechanical properties and fluidity, although slightly inferior compared to Example 5, even when the resin type was changed.

[0109] On the other hand, in Comparative Example 1, the long-short ratio of the carbon fiber (A) in the molded article was small, resulting in poor bending strength. This is because the fiber diameter ratio of the carbon fiber (CF-1) to the carbon fiber (CF-2) in the molding material (C) was small, resulting in an increased proportion of short fibers due to fiber breakage during molding. Similarly, in Comparative Examples 2 and 3, the long-short ratio of the carbon fiber (A) in the molded article was small, resulting in poor mechanical properties. This is because the proportion of carbon fiber (A-2) in the carbon fiber (A) was high, resulting in a low proportion of carbon fiber (A-1) having a long fiber length. In Comparative Examples 4 and 5, since the molding material (C-1) was not included, the carbon fibers in the molded article were short, resulting in poor mechanical properties. In Comparative Example 6, since the molding material (C-2) was not included, the molded article contained few short carbon fibers, resulting in poor fluidity. In Comparative Examples 7 and 8, since the molding material (C-1) was not included, the carbon fibers in the molded article were short, resulting in poor mechanical properties.

Claims

1. A fiber-reinforced resin molded article comprising carbon fiber (A) containing recycled carbon fiber and thermoplastic resin (B), wherein the carbon fiber (A) is present in an amount of 5 to 40 parts by weight per 100 parts by weight of the total of carbon fiber (A) and thermoplastic resin (B), and the carbon fiber (A) is characterized in that 1,000 carbon fibers (A) randomly selected from the molded article have a fiber length ratio of 2 or more and 20 or less as shown in the following formula 1. Ratio of fiber length to short fiber length = Σ(L) ０．６ ) / Σ(L ０．１ )...(Formula 1) L ０．６ : Fiber length (mm) of fibers with a fiber length of 0.6 mm or more L ０．１ : Length (mm) of fibers with a fiber length of 0.1 mm or less

2. The fiber-reinforced resin molded product according to claim 1, characterized in that 1,000 carbon fibers (A) randomly selected from the molded product constitute 15% or less of the short fiber ratio shown in the following formula 2. Short fiber ratio = Σ(L) ０．１ ) / Σ(Li)×100(%) ...(Formula 2) L ０．１ : Length (mm) of fibers with a fiber length of 0.1 mm or less Li: Fiber length of each fiber (mm)

3. The fiber-reinforced resin molded article according to claim 1, characterized in that 1,000 carbon fibers (A) randomly selected from the molded article have a fiber length distribution of 1.4 or more as shown in the following formula 3. Spread of fiber length distribution = (Σ(Li ２ ) / Σ(Li)) / (ΣLi / 1000)...(Formula 3) Li: Fiber length of each fiber (mm)

4. The carbon fiber (A) contained in the fiber reinforced resin molded product has a Raman shift of 1360 cm －１ The maximum value I of the Raman scattering intensity on the surface of the carbon fiber that appears near 1360 , a Raman shift of 1480 cm －１ The minimum value I of the Raman scattering intensity on the surface of the carbon fiber that appears near 1480 , a Raman shift of 1580 cm －１ The maximum value I of the Raman scattering intensity on the surface of the carbon fiber that appears near 1580 Ratio of, I 1360 / I 1580 And I 1480 / I 1580 Contains two types of carbon fibers (A-1) and carbon fiber (A-2) with different values, and the carbon fiber (A-2) has a larger or the same value of I 1360 / I 1580 And a smaller value of I 1480 [ ] / I 1580 The fiber reinforced resin molded product according to claim 1, characterized in that

5. The fiber-reinforced resin molded product according to claim 4, wherein, among the carbon fibers (A) contained in the fiber-reinforced resin molded product, the ratio of the number of carbon fibers (A-1) to the number of carbon fibers (A-2) of 0.6 mm or longer is 100:0 to 50:

50.

6. The fiber-reinforced resin molded article according to claim 4, characterized in that it contains 10 to 70 parts by weight of the carbon fiber (A-2) per 100 parts by weight of the carbon fiber (A).

7. The fiber-reinforced resin molded article according to claim 4, characterized in that the ratio of the fiber diameter φ(A-1) of the carbon fiber (A-1) to the fiber diameter φ(A-2) of the carbon fiber (A-2), φ(A-1) / φ(A-2), is 1.2 or more and 2.0 or less.

8. A fiber-reinforced resin molding material (C) comprising carbon fibers (A) and thermoplastic resin (B), wherein the fiber-reinforced resin molding material (C-1) comprises carbon fibers (CF-1) having a fiber length of 3 mm or more and 10 mm or less and oriented in the longitudinal direction of the molding material and thermoplastic resin (B), and a fiber-reinforced resin molding material (C-2) comprising short fibrous carbon fibers (CF-2) and thermoplastic resin (B), characterized in that the ratio of the fiber diameter φ(CF-1) of carbon fibers (CF-1) to the fiber diameter φ(CF-2) of carbon fibers (CF-2), φ(CF-1) / φ(CF-2), is 1.2 or more and 2.0 or less.

9. The fiber-reinforced resin molding material according to claim 8, characterized in that 1,000 carbon fibers (CF-2) randomly selected from the fiber-reinforced resin molding material (C-2) have a fiber length of 0.1 mm or more and 0.4 mm or less as shown in the following formula 4. The fiber length of carbon fiber (CF-2) = Σ(Li) / 1000 ...(Formula 4) Li: Length of each fiber (mm)

10. The fiber-reinforced resin molding material (C-1) is characterized in that, in addition to carbon fibers (CF-1) and thermoplastic resin (B), it contains a compound (D) different from the thermoplastic resin (B) that is present filling the spaces between each fiber of the carbon fibers (CF-1), as described in claim 8.

11. The fiber-reinforced resin molding material according to claim 8, characterized in that the carbon fiber (CF-2) includes recycled carbon fiber.