JP5962306B2 - Carbon fiber reinforced resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a carbon fiber reinforced resin composition and a molded product thereof. More specifically, an object of the present invention is to provide a carbon fiber reinforced resin composition capable of obtaining a molded product excellent in mechanical properties, surface appearance, low water absorption, and the like, and the molded product.

  It is generally known to blend fibrous fillers such as glass fibers and carbon fibers as a means for improving the mechanical properties of thermoplastic resins. As a general blending technique, a technique in which a fiber reinforced resin composition is obtained by melt-kneading a thermoplastic resin and chopped strands (short fibers) of fibers in an extruder is used.

  However, in recent years, the demand for higher performance of plastics has been advanced, and rigidity equivalent to that of metals has been demanded. In order to achieve rigidity equivalent to that of metal, it is necessary to maintain a long fiber length by highly filling fiber fillers such as glass fiber and carbon fiber. However, when glass fiber is used, rigidity equivalent to metal is realized. It was difficult to do. Further, in the technique of melt kneading in an extruder using a fibrous filler, there are many cases such as fiber breakage due to shear during melt kneading, deterioration of resin due to shearing heat generated by a large amount of fibrous filler, etc. There is a problem, and there is a limit to improving the performance of the technique of melt-kneading the thermoplastic resin and the fibrous filler with an extruder.

  In addition, as a required performance, an excellent appearance that improves designability as well as rigidity equivalent to metal has been demanded. However, the molded product obtained by the method of highly filling the fibrous filler, particularly when carbon fiber is used as the fibrous filler, has undulating irregularities even if it is highly glossy, and the appearance deteriorates. For this reason, it was difficult to achieve both mechanical properties and appearance / design.

  On the other hand, a method of adding specific carbon fibers to nylon 6 has been proposed for the purpose of reducing the weight and increasing the rigidity (for example, see Patent Document 1). However, although weight reduction and high rigidity using a carbon fiber are achieved, waviness-like irregularities are generated and the appearance tends to deteriorate significantly, and there are problems in appearance and design. Moreover, the method of adding a specific carbon fiber to aromatic nylon (MXD6) for the purpose of weight reduction and high rigidity is proposed (for example, refer patent document 2). However, although weight reduction and high rigidity using carbon fibers are achieved in the same manner, undulating irregularities tend to occur and the appearance tends to deteriorate significantly, and there are problems with appearance and design. In addition, a technique for improving the sliding characteristics by adding a filler to a specific polyamide resin has been proposed (for example, see Patent Document 3). However, there is no description about waviness-like irregularities, and although there is a description of carbon fiber, there is no description of implementation and no excellent effect associated therewith. Furthermore, a method for improving impact resistance and surface gloss by adding a specific compound, a filler and carbon fiber in combination to a specific polyamide resin has been proposed (for example, see Patent Document 4). However, although there is no description regarding the wavy unevenness although it is excellent in gloss, there is no description of implementation although there is a description of carbon fiber, and there is no description about the excellent effect associated therewith.

  As described above, in the resin composition, various contrivances have been tried in terms of raw materials such as polymer raw materials and fibrous fillers, but metal equivalent rigidity can be obtained, and excellent appearance and design can be obtained. The fact is that there is no known technique.

JP 2006-1964 (Claim 4) JP 2006-1965 A (Claim 3) JP-A-7-228774 (Claim 1) JP 2010-209247 A (Claim 14)

  This invention solves the said subject, and makes it the subject to provide the carbon fiber reinforced resin composition which can obtain the molded article which has the outstanding mechanical characteristics, external appearance, and designability by carbon fiber reinforcement. It is.

The present invention has been obtained as a result of intensive studies by the present inventors in order to solve the above problems, and has the following configuration.
(1) A carbon fiber reinforced resin composition comprising (B) 10 to 300 parts by weight of carbon fiber and (C) 1 to 40 parts by weight of mica with respect to 100 parts by weight of (A) thermoplastic polyamide resin. The difference between the melting point (Tm) of the thermoplastic polyamide resin obtained by thermal analysis using a differential scanning calorimeter (DSC) and the exothermic peak temperature (Tc) of the temperature-falling crystallization is 0 ° C. or higher and 40 ° C. or lower. The carbon fiber reinforced resin composition characterized by being.
(2) The carbon fiber reinforced resin composition according to (1), wherein the blended amount of (B) carbon fiber is 50 to 150 parts by weight.
(3) The carbon fiber reinforced resin composition according to (1) or (2), wherein the average particle size of (C) mica is 0.1 to 50 μm .
(4) The carbon fiber reinforced resin composition according to any one of (1) to (3), wherein the strand strength of the (B) carbon fiber is 1 to 5 GPa.
(5) A molded product obtained by molding the carbon fiber reinforced resin composition according to any one of (1) to (4).
(6) The molded article according to (5), wherein an arithmetic average height (Wa) value of the undulation curve is 3.0 μm or less.

  According to the carbon fiber reinforced resin composition of the present invention, while providing mechanical properties such as flexural modulus and bending strength, the surface appearance (swelled irregularities) is excellent, and a molded article having low water absorption is provided. be able to. Therefore, in addition to mechanical characteristics, it can be suitably used for various applications such as automobile parts, electrical / electronic parts, building members, and sporting goods parts that require appearance and design.

  The carbon fiber reinforced resin composition of the present invention will be specifically described below.

  The (A) thermoplastic polyamide resin used in the carbon fiber reinforced resin composition of the present invention is not particularly limited as long as it is a resin exhibiting thermoplasticity. The polyamide has an amide bond in the repeating structure of the polymer. If it is, it will not specifically limit.

  Examples of the polyamide resin include homopolyamides and copolyamides obtained by polymerizing monomers such as lactam, aminocarboxylic acid and / or diamine and dicarboxylic acid. Two or more of these may be blended.

  The lactam is preferably a lactam having 6 to 12 carbon atoms, and examples thereof include ε-caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. The aminocarboxylic acid is preferably an aminocarboxylic acid having 6 to 12 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid. And 13-aminotridecanoic acid. Examples of the diamine include aliphatic diamines such as tetramethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethyle diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, 1,3-bisaminomethylcyclohexane, Examples include alicyclic diamines such as 1,4-bisaminomethylcyclohexane, aromatic diamines such as m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, dodecanedioic acid, 1,1,3-tridecane diacid. Examples thereof include aliphatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.

  (A) Specific examples of the thermoplastic polyamide resin include, for example, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene Bacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl- 4-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polyun Camethylene hexahydroterephthalamide (nylon 11T (H)), polyundecamide (nylon 11), polydodecamide (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMDT), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene Examples thereof include isophthalamide (nylon 6I), polymetaxylylene adipamide (nylon MXD6), and copolymers thereof. Among these, nylon 9T, nylon 10T, and copolymer polyamides thereof are preferable from the viewpoints of moldability and surface appearance. Furthermore, it is also practically preferable to blend two or more of these (A) thermoplastic polyamide resins according to necessary properties such as impact resistance and molding processability.

  The polymerization degree of these (A) thermoplastic polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml is 1.5 to 7.0. The thing of the range is preferable and the range of 2.0-6.0 is especially preferable.

  In the present invention, a copper compound is preferably used as an additive for improving long-term heat resistance together with (A) the thermoplastic polyamide resin. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The compounding amount of the copper compound is preferably 0.01 to 2 parts by weight and more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyamide resin. If it is 0.01-2 weight part, long-term heat resistance can be improved, suppressing release | extrication of metallic copper at the time of melt molding, and suppressing coloring of a molded article. It is also possible to add an alkali halide in combination with a copper compound. Examples of the alkali halide compound include potassium iodide and sodium iodide.

  There is no restriction | limiting in particular as (B) carbon fiber used for the carbon fiber reinforced resin composition of this invention, Well-known various carbon fibers can be mentioned. Examples thereof include carbonaceous fibers and graphite fibers produced using polyacrylonitrile (PAN), pitch, rayon, lignin, hydrocarbon gas, and fibers obtained by coating these fibers with metal. Among these, PAN-based carbon fibers can be preferably used because of excellent mechanical property improvement effects. (B) Carbon fiber is usually in the form of chopped strand, roving strand, milled fiber, etc., and generally has a diameter of 15 μm or less, preferably 5 to 10 μm.

  The form of (B) carbon fiber used in the present invention is not particularly limited, but it is used in the form of a bundle of several thousand to several hundred thousand carbon fibers or a pulverized milled form. For the carbon fiber bundle, it is possible to apply a roving method using continuous fibers directly or a method using chopped strands cut to a predetermined length.

  The (B) carbon fiber used in the present invention is preferably a chopped strand, and the number of filaments of the carbon fiber strand that is a precursor of the chopped carbon fiber is preferably 1,000 to 150,000. If the number of filaments of the carbon fiber strand is 1,000 to 150,000, the stability in the production process can be improved and the manufacturing cost can be suppressed.

  The strand elastic modulus of (B) carbon fiber used in the present invention is not particularly limited, but is preferably 150 to 1000 GPa. If the strand elastic modulus of the carbon fiber is 150 GPa or more, the mechanical properties of the molded product can be further improved. 180 GPa or more is more preferable, 200 GPa or more is more preferable, and 220 or more is more preferable. On the other hand, if the strand elastic modulus of the carbon fiber is 1000 GPa or less, the moldability is excellent and the production cost can be suppressed. 700 GPa or less is more preferable, 500 GPa or less is more preferable, and 280 GPa or less is more preferable.

  The strand strength of the (B) carbon fiber used in the present invention is not particularly limited, but is preferably 1 to 10 GPa. When the strand strength of the carbon fiber is 1 GPa or more, the mechanical properties of the molded product can be further improved. 2 GPa or more is more preferable, and 3.5 GPa or more is more preferable. On the other hand, if the strand strength of the carbon fiber is 10 GPa or less, the undulating unevenness of the molded product can be reduced, and the surface appearance / design can be further improved. 8 GPa or less is more preferable, and 5.0 GPa or less is more preferable.

  Here, (B) the strand elastic modulus and the strand strength of the carbon fiber are the elasticity of the strand produced by impregnating and curing an epoxy resin to a continuous fiber bundle composed of 3,000 to 90,000 carbon fiber single fibers. The rate and strength are values obtained by subjecting a strand test piece to a tensile test according to JIS R7601.

  The surface of the (B) carbon fiber used in the present invention may be oxidized to improve the adhesion between the (A) thermoplastic polyamide resin and the (B) carbon fiber. Examples of the oxidation treatment include surface oxidation treatment by energization treatment, oxidation treatment in an oxidizing gas atmosphere such as ozone, and the like.

  Further, (B) a carbon fiber surface with a coupling agent or a sizing agent attached thereto may be used for the purpose of improving the wettability of the resin and improving the handleability. Examples of the coupling agent include amino-based, epoxy-based, chloro-based, mercapto-based, and cationic silane coupling agents, and amino-based silane coupling agents can be preferably used. Examples of the sizing agent include a sizing agent containing at least one selected from a maleic anhydride compound, a urethane compound, an acrylic compound, an epoxy compound, a phenol compound, and derivatives of these compounds. A sizing agent containing a compound or an epoxy compound can be preferably used. (B) The content of the sizing agent in the carbon fiber is preferably 0.1 to 10.0% by weight, more preferably 0.3 to 8.0% by weight, and 0.5 to 6.0% by weight. Is more preferable. If the content of the sizing agent is 0.1 to 10.0% by weight, a carbon fiber that is superior in resin wettability and handleability can be obtained.

  In addition, as a method of applying a sizing agent to the carbon fiber strand (B) used in the present invention and further forming a chopped carbon fiber, for example, a method adopted in a glass fiber chopped strand in JP-B-62-9541 Alternatively, methods described in JP-A-62-244606, JP-A-5-261729, and the like can be applied.

  The blending amount of (B) carbon fiber in the present invention is 10 to 300 parts by weight with respect to 100 parts by weight of (A) thermoplastic polyamide resin. (B) When the blending amount of the carbon fiber is less than 10 parts by weight, the mechanical strength of the molded product is lowered. 20 parts by weight or more is preferable, 30 parts by weight or more is more preferable, and 50 parts by weight or more is more preferable. On the other hand, when the blending amount of (B) carbon fiber exceeds 300 parts by weight, the moldability and the surface appearance of the molded product are deteriorated. 250 parts by weight or less is preferable, 200 parts by weight or less is more preferable, and 150 parts by weight or less is more preferable.

Although the weight average fiber length of (B) carbon fiber in a carbon fiber reinforced resin composition is not specifically limited, It is preferable that it is the range of 0.1-0.5 mm. (B) If the weight average fiber length of carbon fiber is 0.1 mm or more, the impact strength and bending elastic modulus of the molded product can be further improved. 0.125 mm or more is more preferable, and 0.15 mm or more is more preferable. On the other hand, if the weight average fiber length of (B) carbon fiber is 0.5 mm or less, the surface appearance of the molded product can be further improved. 0.45 mm or less is more preferable, and 0.40 mm or less is more preferable. Here, (B) the weight average fiber length of the carbon fiber is obtained by dissolving the pellet obtained from the carbon fiber reinforced resin composition in a solvent in which the (A) thermoplastic polyamide resin is dissolved, and then filtering and washing. The residue is obtained by observing the residue with an optical microscope and measuring the length of 1000 fibers to the weight average fiber length. Specifically, about 10 g of carbon fiber reinforced resin composition pellets are placed in a crucible, steamed until no flammable gas is generated on an electric stove, and then fired in an electric furnace set at 500 ° C. for an additional hour. By doing so, only carbon fiber residue is obtained. Observe an image of the residue magnified 50 to 100 times with an optical microscope, measure the length of 1000 randomly selected, and use the measured value (mm) (2 decimal places are significant figures) Calculation is based on the following formula 1 or formula 2.
(Weight average fiber length (Lw)) = Σ (Wi × Li) / ΣWi
= Σ (π × ri ² × Li × ρ × ni × Li) / Σ (π × ri ² × Li × ρ × ni) (Formula 1)
Here, Li, ni, Wi, ri, ρ, and π are as follows, respectively, and the cross-sectional shape of the carbon fiber approximates a perfect circle of the fiber diameter ri.
(Li: fiber length of carbon fiber, ni: number of carbon fibers of fiber length Li, Wi: weight of carbon fiber of fiber length Li, ri: fiber diameter of carbon fiber of fiber length Li, ρ: density of carbon fiber, π: Pi ratio)
When the fiber diameter ri and the density ρ are constant, the above formula 1 is approximated as follows, and the weight average fiber length can be obtained by the formula 2.
(Weight average fiber length (Lw)) = Σ (Li ² × ni) / Σ (Li × ni) (Formula 2)

  Examples of the method for setting the weight average fiber length of (B) carbon fibers in the carbon fiber reinforced resin composition in the above range include, for example, a method for producing a carbon fiber reinforced resin composition described later, for example, melting by a twin screw extruder. Examples thereof include a method of selecting kneading conditions so that the carbon fibers are not damaged excessively during kneading.

  The carbon fiber reinforced resin composition of the present invention is obtained by thermal analysis using a differential scanning calorimeter (DSC). (A) Melting point (Tm) of thermoplastic polyamide resin and exothermic peak temperature (Tc) of temperature drop crystallization Difference, that is, Tm−Tc is important to be 0 ° C. or more and 50 ° C. or less.

  By setting Tm-Tc to 50 ° C. or lower, crystallization proceeds in a short time and the productivity is excellent, and a molded product with less undulations can be obtained. Tm-Tc is preferably 40 ° C. or lower. On the other hand, when Tm−Tc is set to 0 ° C. or higher, melt processing molding is facilitated. Tm-Tc is preferably 10 ° C. or higher. As a method of setting Tm-Tc to 50 ° C. or lower, (A) a method using a polyamide resin having such thermal characteristics as the thermoplastic polyamide resin can be mentioned. Examples of the thermoplastic polyamide resin (A) having a Tm-Tc of 50 ° C. or lower include polyamide 9T, polyamide 9T / 8MT, polyamide 10T, polyamide 12T, polyamide 10T / 1012, polyamide 6T / 66, polyamide 6T / 6I, Examples thereof include polyamide 46, polyamide 66, and polyamide 5T / 6T. Polyamide 9T, polyamide 9T / 8MT, and polyamide 10T are more preferable, and polyamide 9T / 8MT is more preferable. “/” Represents a copolymer and the same applies hereinafter.

  Here, the melting point (Tm) of the thermoplastic polyamide resin (A) in the present invention is the melting when measured by increasing the temperature from 30 ° C. to 10 ° C./min using an EXSTAR DSC6000 manufactured by Seiko Instruments Inc. It means endothermic peak temperature. Although there is no restriction | limiting in particular in Tm value, From a heat resistant viewpoint, 150 degreeC or more is preferable, 200 degreeC or more is more preferable, and 250 degreeC or more is further more preferable. On the other hand, from the viewpoint of suppressing decomposition of the resin during melt molding, 350 ° C. or lower is preferable, 300 ° C. or lower is more preferable, and 280 ° C. or lower is further preferable.

  On the other hand, the exothermic peak temperature (Tc) of the temperature drop crystallization of the thermoplastic polyamide resin in the present invention is 10 ° C. from the state where the thermoplastic polyamide resin is completely melted using EXSTAR DSC6000 manufactured by Seiko Instruments Inc. It means the temperature at the top of the crystallization exothermic peak when the temperature is lowered at a rate of / min.

  The carbon fiber reinforced resin composition of the present invention may further contain (C) a granular filler. (C) By mix | blending a granular filler, the surface external appearance of a molded article can be improved more and the curvature and molding shrinkage of a molded article can be reduced. (C) As the granular filler, any filler such as plate, powder, and granule other than the fibrous filler such as glass fiber and carbon fiber can be used.

  (C) As the plate-like filler, for example, silicates such as talc, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, metal compounds such as magnesium oxide, alumina, zirconium oxide, iron oxide, Carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, hydroxides such as boron nitride, calcium phosphate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass flakes Non-fibrous fillers such as glass powder, glass balloons, carbon black and silica, graphite, and smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and saconite, vermiculite, halo Various clay minerals such as site, kanemite, kenyanite, zirconium phosphate, titanium phosphate, etc., layered layers represented by swellable mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica Silicate may be mentioned. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions.

  In the present invention, two or more kinds of (C) granular fillers may be used in combination. These (C) particulate fillers are preferably treated with a coupling agent such as silane or titanate, or other surface treatment agent, and when treated with an epoxysilane or aminosilane coupling agent. Is particularly preferable because it can exhibit more excellent mechanical properties.

  Among the granular fillers (C) in the present invention, mica, talc, kaolin, clay, glass flake, carbon black, graphite, montmorillonite and the like are preferably used, mica, talc and glass flake are more preferable, and mica is more preferable. Talc, and more preferably mica. By using mica, the surface appearance and water absorption characteristics of the molded product can be further improved.

  (C) The particle diameter of the granular filler is preferably in the range of an average particle diameter of 0.1 to 50 μm. When the average particle diameter is 0.1 μm or more, the surface appearance of the molded product is further improved. 0.5 μm or more is more preferable, and 1 μm or more is more preferable. On the other hand, when the average particle size is 50 μm or less, mechanical properties such as Charpy impact are further improved. 30 μm or less is more preferable, and 20 μm or less is more preferable. Here, the average particle diameter is an arithmetic average diameter obtained by measurement by a laser diffraction / scattering method, and is a volume average particle diameter. Here, the average particle diameter of (C) granular filler is a volume average particle diameter measured by a microtrack laser diffraction method. Specifically, it can be measured by a wet method using Microtrack MT-3000 manufactured by Nikkiso Co., Ltd.

  The blending amount of the (C) granular filler in the present invention is preferably 1 to 40 parts by weight with respect to 100 parts by weight of (A) the thermoplastic polyamide resin. (C) If the compounding quantity of a granular filler is 1 weight part or more, the surface external appearance of a molded article will improve more. 3 parts by weight or more is more preferable, and 5 parts by weight or more is more preferable. On the other hand, when the blending amount of the (C) granular filler is 40 parts by weight or less, the balance between the improvement of the surface appearance of the molded product and the excellent moldability is further improved. 30 parts by weight or less is more preferable, and 20 parts by weight or less is more preferable.

  In the carbon fiber reinforced resin composition of the present invention, as long as the effects of the present invention are not impaired, a stabilizer, a release agent, an ultraviolet absorber, a colorant, a flame retardant, a flame retardant aid, an anti-dripping agent, a lubricant, Additives such as fluorescent brighteners, phosphorescent pigments, fluorescent dyes, flow modifiers, impact modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, (B) Fillers other than carbon fibers and (C) granular fillers, (A) thermoplastic resins other than thermoplastic polyamide resins, thermosetting resins, and the like can be blended.

  In the present invention, any stabilizer that is used as a stabilizer for thermoplastic resins can be used. Specific examples include antioxidants and light stabilizers. By blending these stabilizers, it is possible to obtain a carbon fiber reinforced resin composition and a molded product that are more excellent in mechanical properties, moldability, heat resistance and durability.

  In the present invention, as the mold release agent, any of those used for mold release agents for thermoplastic resins can be used. Specific examples include fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, and modified silicones. By blending these release agents, a molded product that is superior in mechanical properties, moldability, heat resistance, and durability can be obtained.

  In the present invention, the flame retardant is at least one kind of flame retardant selected from brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants. It is preferable to use any two or more kinds of flame retardants selected from the above flame retardants in that a flame retardant can be used and excellent in flame retardancy and mechanical properties.

  In the present invention, specific examples of brominated flame retardants include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy). ) Ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisph Nord-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A-carbonate oligomer or polymer, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneopene Glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo terephthalic imide.

  In the present invention, specific examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.

  In the present invention, as a specific example of the phosphorus-based flame retardant, generally used phosphorus-based flame retardant can be used, for example, organic phosphorus compounds such as phosphate ester, condensed phosphate ester, polyphosphate, In view of excellent fluidity, mechanical properties and flame retardancy, one or more of condensed phosphate ester, polyphosphate and red phosphorus is preferable, and condensed phosphate ester is more preferable. An aromatic condensed phosphate ester is more preferable. Examples of the aromatic condensed phosphate ester include resorcinol polyphenyl phosphate and resorcinol poly (di-2,6-xylyl) phosphate.

  In the present invention, examples of the nitrogen compound-based flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea, etc. In terms of excellent flame retardancy and mechanical properties, a nitrogen-containing heterocyclic compound is preferable, among which a triazine compound is preferable, melamine cyanurate or melamine isocyanurate is more preferable, and among these, cyanuric acid or isocyanuric acid and a triazine compound are preferable. Adducts are preferred, and mention may be made of adducts having a composition of usually 1 to 1 (molar ratio), optionally 1 to 2 (molar ratio). When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

Examples of the silicone flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include resins having a three-dimensional network structure formed by combining RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 structural units. Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group at the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof And so on.

  In the present invention, as other inorganic flame retardants, for example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, Tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, tungstic acid metal salt, tungsten And oxides of metal and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, swellable graphite, and the like. In the present invention, magnesium hydroxide, a fluorine-based compound, and swellable graphite are preferable, and a fluorine-based compound is more preferable in terms of excellent flame retardancy and mechanical properties. Examples of the fluorine compound include polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, Hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer and the like are preferable, and polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferable.

  Although the manufacturing method of the fiber reinforced resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, (A) thermoplastic polyamide resin, (B) carbon fiber, as needed The other components (A) above the melting point (Tm) of the thermoplastic polyamide resin are preferably used, such as a method of uniformly melting and kneading with a single or twin screw extruder or a method of removing the solvent after mixing in a solution. However, from the viewpoint of productivity, a method of uniformly melting and kneading with a single-screw or twin-screw extruder is preferable, and a twin-screw extruder is used because a resin composition excellent in fluidity and mechanical properties can be obtained. A method of uniformly melt-kneading is more preferable. In particular, when the screw length is L and the screw diameter is D, a melt kneading method using a twin screw extruder with L / D> 30 is particularly preferable. The screw length here refers to the length from the position where the screw base material is supplied to the tip of the screw.

  In the present invention, in the case of melt kneading, for example, a method of charging each component is performed by using an extruder having two charging ports, and (A) a thermoplastic polyamide resin from a main charging port installed on the screw root side, ( B) A method of supplying carbon fiber and other components as required, or (A) thermoplastic polyamide resin and other components as required from the main input port, and installed between the main input port and the extruder tip (B) a method of supplying carbon fiber and other components as needed from the sub-inlet and melt-kneading, and (A) thermoplastic polyamide resin and other components as required from the main inlet, And (B) a method of supplying carbon fiber and other components as necessary. In terms of excellent mechanical properties and production stability, (A) thermoplastic polyamide resin and other components are supplied as needed from the main input port, and a sub-input port installed between the main input port and the extruder tip. (B) A method of supplying carbon fiber and melt-kneading is preferable.

  In order to make the weight average fiber length of (B) carbon fibers in the carbon fiber reinforced resin composition within the above-mentioned range, (A) a thermoplastic polyamide resin and other components as necessary are supplied from the main input port. (B) A method of supplying carbon fiber from a sub-inlet installed between the inlet and the extruder tip and melting and kneading is preferable, and it is more possible to adjust the mixing time and the rotation speed so that the carbon fiber is not damaged too much. preferable. Further, although depending on the type of (A) thermoplastic polyamide resin, a method of setting the plasticizing temperature of the molten resin at the time of melt-kneading to be high is preferable in order to reduce the pressure of the molten resin.

  The carbon fiber reinforced resin composition of the present invention can be manufactured into various molded articles by molding pellets obtained by cutting the extruded strand, which is usually melt-kneaded as described above. As a molding method, injection molding is generally used. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained by using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, or ultra-high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for forming.

  Moreover, the carbon fiber reinforced resin composition of the present invention can also be used in the form of various modified extruded products, sheets, films, etc. by extrusion molding. For forming a sheet or film, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the carbon fiber reinforced resin composition of the present invention can be made into a hollow molded product by rotational molding, blow molding or the like.

The weight average fiber length of the (B) carbon fiber in the carbon fiber reinforced resin molded article of the present invention is not particularly limited, but is preferably in the range of 0.05 to 0.5 mm. (B) If the weight average fiber length of the carbon fiber is 0.05 mm or more, the impact strength and the flexural modulus of the molded product can be further improved. 0.07 mm or more is more preferable, and 0.1 mm or more is more preferable. On the other hand, if the weight average fiber length of (B) carbon fiber is 0.5 mm or less, the surface appearance of the molded product can be further improved. 0.45 mm or less is more preferable, and 0.4 mm or less is more preferable. Here, (B) the weight average fiber length of the carbon fibers is obtained by dissolving the carbon fiber reinforced resin molded article with a solvent in which the (A) thermoplastic polyamide resin dissolves, and then filtering and washing, and then removing the residue with an optical microscope. It is obtained by calculating the weight average fiber length by observing at 1000 and measuring the length of 1000 pieces. Specifically, about 10 g of a carbon fiber reinforced resin molded product is placed in a crucible, steamed until no flammable gas is generated on an electric stove, and then fired in an electric furnace set at 500 ° C. for another hour. To obtain only carbon fiber residues. Observe an image of the residue magnified 50 to 100 times with an optical microscope, measure the length of 1000 randomly selected, and use the measured value (mm) (2 decimal places are significant figures) Calculation is based on the following formula 1 or formula 2.
(Weight average fiber length (Lw)) = Σ (Wi × Li) / ΣWi
= Σ (π × ri ² × Li × ρ × ni × Li) / Σ (π × ri ² × Li × ρ × ni) (Formula 1)
Here, Li, ni, Wi, ri, ρ, and π are as follows, respectively, and the cross-sectional shape of the carbon fiber approximates a perfect circle of the fiber diameter ri.
(Li: fiber length of carbon fiber, ni: number of carbon fibers of fiber length Li, Wi: weight of carbon fiber of fiber length Li, ri: fiber diameter of carbon fiber of fiber length Li, ρ: density of carbon fiber, π: Pi ratio)
When the fiber diameter ri and the density ρ are constant, the above formula 1 is approximated as follows, and the weight average fiber length can be obtained by the formula 2.
(Weight average fiber length (Lw)) = Σ (Li ² × ni) / Σ (Li × ni) (Formula 2)

  In addition, as a method of setting the weight average fiber length of (B) carbon fiber of the carbon fiber reinforced resin molded article in the above range, for example, (B) the weight average fiber length of the carbon fiber is in the specific range described above. Examples thereof include a method for molding a carbon fiber reinforced resin composition.

  The carbon fiber reinforced resin molded product of the present invention preferably has an arithmetic average height (Wa value) of a waviness curve of 3.0 μm or less. When the Wa value is 3.0 μm or less, waviness-like irregularities observed visually on the surface of the carbon fiber reinforced resin molded product can be reduced, and the surface appearance and design can be further improved. More preferably, it is 2.5 micrometers or less, More preferably, it is 2.0 micrometers or less. Further, the lower limit value of the Wa value is 0 μm and is not particularly limited. The arithmetic average height (Wa value) of the undulation curve here is defined by JISB0601, and a surface roughness measuring device (80 mm × 80 mm × 2 mm square plate product produced by injection molding is used ( ACCRTECH) and the average length (Wa) of the waviness curve obtained by measuring the surface of the molded product at an evaluation length of 20 mm and a test speed of 0.6 mm / sec.

  Examples of the method of setting the Wa value of the carbon fiber reinforced resin molded product in the above range include a method of molding the above-described carbon fiber reinforced resin composition of the present invention.

  In the present invention, the above-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, sports equipment parts, various containers, daily necessities, household goods and sanitary goods. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer , Distributor cap, vapor canister Housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Exterior parts for vehicles, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop housings, chassis and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile phones, mobile PCs, handheld mobiles, etc. Mobile terminal housing, chassis and internal parts, recording medium (CD, DVD, PD, FDD, etc.) drive housing, chassis and internal parts, copier housing, chassis and internal parts, facsimile housing, chassis and internal parts, Electric and electronic parts such as parabolic antennas can be mentioned. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts and housings, chassis parts, refrigerator parts, air conditioner parts, type Examples include home and office electrical product parts such as lighter parts and word processor parts. Also, housings, chassis and internal parts for electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, Variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, Electric and electronic parts such as motor brush holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts Roof panels, heat insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other construction parts, concrete formwork and other civil engineering parts, fishing rod parts, reel housings, spool and body parts, lure parts, coolers Box parts, golf club parts, tennis, badminton, squash racket parts, ski parts, ski stock parts, bicycle frames, pedals, front forks, handlebars, brake brackets, cranks, seat pillars, wheels, special shoes, etc. Parts, boat oars, sports helmets, fence components, golf tees, sports equipment parts such as kendo armor (face) and bamboo swords, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, Water supply parts, toy parts, Bundle bands, clips, fans, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks and other machine parts, seedling pots, vegetation piles, farming stoppers and other agricultural parts, fracture reinforcements, etc. Medical supplies, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, containers such as baskets, hot fill containers, microwave cooking containers cosmetic containers, IC trays, It is useful as stationery, drainage filter, bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on. In particular, it is useful as an interior part for automobiles, exterior parts for automobiles, sports equipment members, and housings, chassis and internal parts for various electric / electronic parts. In particular, the resin composition of the present invention can be used more suitably in applications where water absorption is required, in which the performance of the resin composition is utilized. For example, it is useful for portable electric and electronic equipment cases such as notebook computers, mobile phones, digital video cameras, automobile exterior parts, motorcycle parts, mountaineering equipment, fishing equipment, golf equipment, ski / skate equipment, swimming equipment, and the like.

  The carbon fiber reinforced resin composition and molded product of the present invention can be recycled. For example, after carbon fiber reinforced resin pellets or carbon fiber reinforced resin molded products are pulverized and preferably powdered, additives are blended as necessary and melt-kneaded and molded to obtain carbon fiber reinforced resin molded products. Can be obtained. However, when fiber breakage occurs, it is difficult for a carbon fiber reinforced resin molded product obtained using the fiber to exhibit the same mechanical strength as the carbon fiber reinforced resin molded product of the present invention.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples.

  The following materials were used. Here, Tm and Tc respectively indicate the melting point and the crystallization temperature obtained by measurement by the method described later.

(A) Thermoplastic polyamide resin <A1> Nylon 9T / 8MT resin “Genesta” (registered trademark) N1001D (manufactured by Kuraray Co., Ltd.) (Tm: 262 ° C., Tc: 228 ° C.)
<A2> Nylon 9T / 8MT resin “Genesta” (registered trademark) N1000A (manufactured by Kuraray Co., Ltd.) (Tm: 306 ° C., Tc: 264 ° C.)
<A3> Polyamide 10T / 66 (molar ratio 93/7) (Tm: 294 ° C., Tc: 263 ° C.)
<A4> Polyamide 10T (Tm: 314 ° C., Tc: 283 ° C.)
<A5> Polyamide MXD6 resin “Renny” (registered trademark) # 6002 (manufactured by Mitsubishi Engineering Plastics) (Tm: 238 ° C., Tc: 161 ° C.)
<A6> Polyamide 6 “Amilan” (registered trademark) CM1001 (manufactured by Toray Industries, Inc.) (Tm: 222 ° C., Tc: 167 ° C.)

(B) Carbon fiber <B1> PAN-based carbon fiber “Torayca” (registered trademark) cut fiber TV14-006 (manufactured by Toray Industries, Inc., original yarn T700SC-12K: tensile strength 4.9 GPa, tensile elastic modulus 230 GPa) was used. .
<B2> PAN-based carbon fiber “Torayca” (registered trademark) yarn T800SC-24K (manufactured by Toray Industries, Inc., tensile strength 5.9 GPa, tensile elastic modulus 294 GPa) cut to a fiber length of 6.0 mm with a rotary cutter It was used.
<B3> PAN-based carbon fiber “Torayca” (registered trademark) cut fiber TS15-006 (manufactured by Toray Industries, Inc., original yarn S300C-48K: tensile strength 3.4 GPa, tensile elastic modulus 230 GPa) was used.

(C) Granular filler <C1> Mica: A-11 (manufactured by Yamaguchi Mica, average particle diameter 3 μm)
<C2> Mica: A-21 (Yamaguchi Mica, average particle size 22 μm)
<C3> Mica: A-51S (manufactured by Yamaguchi Mica, average particle size 52 μm)
<C4> Talc: P-6 (Nippon Talc, average particle size 4 μm)
<C5> Glass flake: REFG101 (manufactured by Nippon Sheet Glass Co., Ltd.)

Other glass fiber: T-249 (Nippon Electric Glass Co., Ltd.)

[Example 1-7, Comparative Examples 1-4, Reference Examples 1 to 11]
Using a twin screw extruder (TEX30α manufactured by Nippon Steel Works) with the cylinder temperature set to the temperature shown in Tables 1 and 2 and the screw rotation speed set to 200 rpm, thermoplastic polyamide resin from the main hopper, (C) granular filler Are supplied in the formulation shown in Tables 1-2, and (B) carbon fiber or glass fiber is supplied into the molten resin in the formulation shown in Tables 1-2 using a side feeder, and the strand discharged from the die is submerged in water. Then, it was cooled to a length of 3.0 mm with a strand cutter and pelletized to obtain carbon fiber or glass fiber reinforced resin composition pellets.

  The carbon fiber or glass fiber reinforced resin composition pellets obtained above were vacuum dried at 80 ° C. for 48 hours, and an injection molding machine (SE75DUZ manufactured by Sumitomo Heavy Industries, Ltd.) was used. The mold temperature was set to 80 ° C. (140 ° C. at the time of forming the square plate), the injection speed was set to 100 mm / sec, and the injection pressure was set to the lower limit pressure (minimum filling pressure) +5 MPa.

(1) Measurement of melting point (Tm) and temperature drop crystallization temperature (Tc) About (A) thermoplastic polyamide resin used above, using EXSTAR DSC6000 made by Seiko Instruments Inc. at a rate of 30 ° C. to 10 ° C./min. The melting point (Tm) is obtained from the melting endothermic peak temperature when measured by raising the temperature, and the temperature at the top of the crystallization exothermic peak when the temperature is lowered at a rate of 10 ° C./min from the state where the thermoplastic polyamide resin is completely dissolved. From this, the cooling crystallization temperature (Tc) was determined, and Tm-Tc was calculated from each measured value.

(2) Impact resistance Charpy impact strength (notched) was evaluated at 23 ° C in accordance with ISO179.

(3) Flexural strength and flexural modulus Flexural strength and flexural modulus were evaluated at 23 ° C. according to ISO178.

(4) Specific gravity A dumbbell test piece was molded by an injection molding machine according to ISO178, and the specific gravity of the test piece was measured at room temperature (23 ° C.) according to ISO1183.

(5) Surface Roughness Using an 80 mm × 80 mm × 2 mm square plate obtained by injection molding, using a surface roughness measuring device (manufactured by ACCRTECH), an evaluation length of 8 mm, a test speed of 0.6 mm / sec. The arithmetic average roughness (Ra) value of the surface of the molded product was evaluated under the following measurement conditions.

(6) Surface waviness Using an 80 mm × 80 mm × 2 mm square plate obtained by injection molding, using a surface roughness measuring device (manufactured by ACCRTECH), an evaluation length of 20 mm and a test speed of 0.6 mm / sec. Under the measurement conditions, the arithmetic average height (Wa) value of the waviness curve on the surface of the molded product was evaluated.

(7) Water absorption rate Using the dumbbell test piece prepared in (4) above, a water absorption test was performed in which the sample was allowed to stand in an environment of 80 ° C. and 95% RH and the change in weight with time was measured. The rate was determined. In addition, in the following formula | equation, the weight at the time of drying is an initial weight of the dumbbell test piece before using for a water absorption test.
Water absorption rate (%) = [(95% RH after 1000 hours-dry weight) / dry weight] × 100

(8) Rate of strength reduction during water absorption Using the dumbbell test piece after the water absorption test of (7) above, bending strength was evaluated at 23 ° C. according to ISO178. And the strength reduction rate was calculated | required from the following formula | equation. In addition, in the following formula | equation, the strength at the time of drying is the bending strength of the dumbbell test piece before using for a water absorption test.
Strength reduction rate (%) = [bending strength at drying−bending strength after water absorption test) / bending strength at drying] × 100

(9) Weight average fiber length (Lw)
Using the dumbbell test piece prepared in (4) above, about 10 g of a part of the test piece was cut out, placed in a crucible and steamed until no flammable gas was generated on an electric stove, and then set to 500 ° C. Only a carbon fiber residue was obtained by firing for another hour in the furnace. Observe an image of the residue magnified 50 to 100 times with an optical microscope, measure the length of 1000 randomly selected, and use the measured value (mm) to determine the weight based on the following formula Average fiber length (Lw) was calculated.
Lw (mm) = Σ (Li ² × ni) / Σ (Li × ni)
Here, Li and ni indicate the fiber length of the carbon fiber and the number of carbon fibers having the fiber length Li, respectively.

The carbon fiber reinforced resin compositions shown in Examples 1 to 7 are excellent in Charpy impact strength, bending strength, and flexural modulus, as well as low specific gravity and low surface roughness, which is an index of appearance characteristics, and surface waviness. Both mechanical properties comparable to metals and appearance / design are compatible.

  In Comparative Examples 1 to 4, any of Charpy impact strength, bending strength, flexural modulus, specific gravity, surface roughness and surface waviness is insufficient.

  According to the carbon fiber reinforced resin composition of the present invention, while providing mechanical properties such as flexural modulus and bending strength, the surface appearance (swelled irregularities) is excellent, and a molded article having low water absorption is provided. be able to. Therefore, in addition to mechanical characteristics, it can be suitably used for various applications such as automobile parts, electrical / electronic parts, building members, and sporting goods parts that require appearance and design.

Claims (6)

(A) A carbon fiber reinforced resin composition obtained by blending 10 to 300 parts by weight of carbon fiber and (C) 1 to 40 parts by weight of mica with respect to 100 parts by weight of a thermoplastic polyamide resin. Obtained by thermal analysis using a scanning calorimeter (DSC) (A) The difference between the melting point (Tm) of the thermoplastic polyamide resin and the exothermic peak temperature (Tc) of the temperature-falling crystallization is 0 ° C. or higher and 40 ° C. or lower. A carbon fiber reinforced resin composition characterized by the above. (B) Carbon fiber compounding quantity is 50-150 weight part, The carbon fiber reinforced resin composition of Claim 1 characterized by the above-mentioned. (C) The average particle diameter of mica is 0.1-50 micrometers, The carbon fiber reinforced resin composition of Claim 1 or 2 characterized by the above-mentioned. (B) The carbon fiber reinforced resin composition according to any one of claims 1 to 3, wherein the carbon fiber has a strand strength of 1 to 5 GPa. The molded article formed by shape | molding the carbon fiber reinforced resin composition in any one of Claims 1-4. 6. The arithmetic average height (Wa) value of the undulation curve is 3.0 μm or less.
The molded product described.