JP2017186496A - Carbon fiber reinforced polyamide resin composition and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon fiber reinforced polyamide resin composition capable of obtaining a molded article having low water absorption and excellent mechanical properties and surface appearance. SOLUTION: (A-1) A semi-aromatic polyamide resin having a difference between a melting point and a cooling crystallization peak temperature of 0°C or more and less than 50°C, and (A-2) a difference between the melting point and the cooling crystallization peak temperature is 50. A carbon fiber reinforced polyamide resin composition obtained by blending a polyamide resin having a temperature of not less than 90°C and less than 90°C and a carbon fiber (B), wherein (A-1) and (A-2) are 100 parts by weight in total, (A-1) 50 parts by weight or more and 99 parts by weight or less, (A-2) 1 part by weight or more and 50 parts by weight or less, and (B) 10 parts by weight or more and 100 parts by weight or less. Resin composition. [Selection diagram] None

Description

  The present invention relates to a carbon fiber reinforced polyamide resin composition and a molded article comprising the same.

  As a means for improving the mechanical properties of a thermoplastic resin, it is generally known to blend a fibrous filler such as glass fiber or carbon fiber. As a general blending method of the fibrous filler, there is a method of melt-kneading a thermoplastic resin and a chopped strand (short fiber) of a fiber in an extruder.

  In recent years, the demand for higher performance of plastics has increased, and in addition to mechanical properties equivalent to metals, design properties (good appearance) have been demanded. However, the molded product obtained by blending the fibrous filler is likely to have a decrease in surface appearance due to a decrease in gloss due to the floating of the fibrous filler, and the occurrence of wavy irregularities. It was difficult to achieve both design properties. Further, when the molded article has a high water absorption, a molded article having a low water absorption has been demanded because a reduction in rigidity due to water absorption in a use environment and a warp due to a dimensional change are likely to occur.

  On the other hand, as a carbon fiber reinforced resin composition capable of obtaining a molded product having excellent mechanical characteristics, appearance and design, there is a difference between the melting point (Tm) and the exothermic peak temperature (Tc) of the temperature-falling crystallization. A carbon fiber reinforced resin composition (for example, see Patent Document 1) obtained by blending a thermoplastic polyamide resin of 0 ° C. or higher and 50 ° C. or lower and carbon fiber has been proposed. Although this technique can suppress undulations, there is a problem that the surface roughness is still large. In addition, as a resin composition having excellent moldability, low rigidity and strength at the time of water absorption, and excellent appearance, a polyamide resin having 7 or more carbon atoms per amide group and containing no aromatic ring, A polyamide resin having an aromatic ring and exhibiting crystallinity and a resin composition containing carbon fiber (for example, Patent Document 2) have been proposed. However, a technique for further reducing water absorption and suppressing undulation unevenness is desired. It was done.

  On the other hand, as a carbon fiber reinforced thermoplastic resin composition excellent in mechanical properties and surface appearance, a thermoplastic resin composition containing a thermoplastic resin, carbon fiber, and a titanium compound (see, for example, Patent Document 3) has been proposed. . Although this technique suppresses surface roughness and undulations, there is a problem that mechanical properties are insufficient.

JP 2013-64106 A International Publication No. 2013/077238 International Publication No. 2013/080820

  An object of the present invention is to provide a carbon fiber reinforced polyamide resin composition that solves the above-described problems and that can provide a molded article having low water absorption and excellent mechanical properties and surface appearance.

The present invention mainly has the following configuration.
(1) (A-1) A semi-aromatic polyamide resin having a difference between the melting point and the cooling crystallization peak temperature of 0 ° C. or more and less than 50 ° C., and (A-2) a difference between the melting point and the cooling crystallization peak temperature being 50 ° C. A carbon fiber reinforced polyamide resin composition comprising a polyamide resin of less than 90 ° C. and (B) carbon fiber, wherein (A-1) and (A-2) are 100 parts by weight in total ( Carbon fiber reinforced polyamide resin obtained by blending A-1) 50 parts by weight or more and 99 parts by weight or less, (A-2) 1 part by weight or more and 50 parts by weight or less, and (B) 10 parts by weight or more and 100 parts by weight or less. Composition.
(2) The carbon fiber according to (1), wherein the polyamide resin having a difference between the melting point and the temperature-falling crystallization peak temperature of 50 ° C. or more and less than 90 ° C. has a heat of fusion (ΔHm) of 50 J / g or less. Reinforced polyamide resin composition.
(3) The difference between the (A-1) melting point and the temperature-falling crystallization peak temperature is a semi-aromatic polyamide resin having a difference between 0 ° C. and less than 50 ° C. and (A-2) the difference between the melting point and the temperature-falling crystallization peak temperature is 50 (C) 0.1 parts by weight or more and 5 parts by weight or less of a polyvalent amine compound having 3 or more amino groups in one molecule is further added to 100 parts by weight of the polyamide resin at a temperature of from 0 to 90 ° C. The carbon fiber reinforced polyamide resin composition according to (1) or (2).
(4) The difference between the (A-1) melting point and the cooling crystallization peak temperature is a semi-aromatic polyamide resin having a difference between 0 ° C. and less than 50 ° C., and (A-2) the difference between the melting point and the cooling crystallization peak temperature is 50. The carbon fiber reinforcement according to any one of (1) to (3), wherein the amino terminal group concentration of the carbon fiber reinforced polyamide resin composition is 3 × 10 ⁻⁵ eq / g or more with respect to a polyamide resin having a temperature of ≧ 90 ° C. Polyamide resin composition.
(5) The carbon fiber reinforced polyamide resin composition according to any one of (1) to (4), which has a cooling crystallization peak temperature in each of a range of 220 ° C. or higher and lower than 300 ° C. and a range of 160 ° C. or higher and lower than 220 ° C. .
(6) The carbon fiber-reinforced polyamide resin composition according to any one of (1) to (5), wherein the half crystallization time is 5 seconds or more and 60 seconds or less.
(7) (A-1) A semi-aromatic polyamide resin having a difference between the melting point and the cooling crystallization peak temperature of 0 ° C. or more and less than 50 ° C., and (A-2) a difference between the melting point and the cooling crystallization peak temperature being 50 ° C. It is a manufacturing method of the carbon fiber reinforced polyamide resin composition which mix | blends the polyamide resin below 90 degreeC and (B) carbon fiber, Comprising: With respect to a total of 100 weight part of (A-1) and (A-2), Carbon fiber reinforced polyamide resin composition containing (A-1) 50 parts by weight or more and 99 parts by weight or less, (A-2) 1 part by weight or more and 50 parts by weight or less, and (B) 10 parts by weight or more and 100 parts by weight or less. Manufacturing method.
(8) A molded article comprising the carbon fiber reinforced polyamide resin composition according to any one of (1) to (6).

  According to the carbon fiber reinforced polyamide resin composition of the present invention, it is possible to provide a molded article having low water absorption and excellent mechanical properties and surface appearance.

  The carbon fiber reinforced polyamide resin composition of the present invention is obtained by thermal analysis using a differential scanning calorimeter (DSC), and the difference between (A-1) melting point (Tm) and cooling crystallization peak temperature (Tc) is Semi-aromatic polyamide resin of 0 ° C. or more and less than 50 ° C. (hereinafter sometimes referred to as “(A-1) semi-aromatic polyamide resin”), (A-2) melting point (Tm) and temperature-falling crystallization peak temperature A polyamide resin having a difference from (Tc) of 50 ° C. or higher and lower than 90 ° C. (hereinafter sometimes referred to as “(A-2) polyamide resin”) and (B) carbon fiber are blended. (B) While the mechanical properties can be improved by the carbon fiber, the surface appearance tends to be lowered as described above. The (A-1) semi-aromatic polyamide resin used in the present invention has low water absorption, and further, when combined with (A-2), results from the difference between the melting point (Tm) and the temperature-falling crystallization peak temperature (Tc). Using the characteristics, during the molding, (A-1) the semi-aromatic polyamide resin is crystallized at an early stage, the shrinkage in the thickness direction is suppressed to reduce the surface waviness, and (A-2) the polyamide resin is (A -1) It can solidify more slowly than a semi-aromatic polyamide resin to improve mold transferability and reduce surface roughness.

  The difference between the melting point (Tm) and the temperature-falling crystallization peak temperature (Tc) of the (A-1) semi-aromatic polyamide resin in the present invention, that is, Tm-Tc is 0 ° C. or more and less than 50 ° C. (A-1) When the Tm-Tc of the semi-aromatic polyamide resin is 50 ° C. or higher, waviness-like irregularities (surface waviness) on the surface of the molded article increase, and the surface appearance deteriorates. From the viewpoint of further reducing the surface waviness of the molded product, Tm-Tc of the (A-1) semi-aromatic polyamide resin is preferably less than 45 ° C, more preferably less than 40 ° C. On the other hand, from the viewpoint of further reducing the surface roughness of the molded product, Tm-Tc of the (A-1) semi-aromatic polyamide resin is preferably 20 ° C or higher, more preferably 25 ° C or higher, and further preferably 30 ° C or higher. .

  Here, the melting point (Tm) of the (A-1) semi-aromatic polyamide resin in the present invention refers to the temperature at the top of the melting endothermic peak, and in accordance with JIS K7121 (1987), (A-1) half It means the melting endothermic peak temperature in the DSC curve when the amount of heat is measured by heating the aromatic polyamide resin at a rate of 30 ° C. to 10 ° C./min. For the measurement of the melting point, a differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used. When two or more melting endothermic peaks are observed, the melting endothermic peak temperature existing on the higher temperature side is defined as Tm. Tm is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 280 ° C. or higher from the viewpoint of heat resistance. On the other hand, from the viewpoint of suppressing decomposition during melt molding, 350 ° C. or lower is preferable, 330 ° C. or lower is more preferable, and 320 ° C. or lower is further preferable.

  On the other hand, the temperature drop crystallization peak temperature (Tc) of the (A-1) semi-aromatic polyamide resin in the present invention refers to the temperature at the top of the crystallization exothermic peak, and in accordance with JIS K7121 (1987), (A -1) The temperature of the semi-aromatic polyamide resin is increased from 30 ° C. to a temperature 30 ° C. higher than the end temperature of the melting endothermic peak at a rate of 10 ° C./min. It means the temperature at the top of the crystallization exothermic peak in the DSC curve when the amount of heat is measured by lowering the temperature. A differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used to measure the temperature-falling crystallization peak temperature. When two or more cooling crystallization peaks are observed, the crystallization exothermic peak temperature existing on the higher temperature side is defined as Tc. Tc is not particularly limited as long as the difference from Tm is less than 50 ° C., but is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and more preferably 250 ° C. or higher from the viewpoint of further reducing the surface waviness of the molded product. preferable. On the other hand, from the viewpoint of further reducing the surface roughness of the molded product, it is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and further preferably 270 ° C. or lower.

  Examples of the semi-aromatic polyamide resin having Tm-Tc of less than 50 ° C. include polyamide 9T, polyamide 9T / 8MT, polyamide 10T, polyamide 12T, polyamide 10T / 1012, polyamide 6T / 66, polyamide 6T / 6I, and polyamide 5T. / 6T and the like. Polyamide 9T, polyamide 9T / 8MT, and polyamide 10T are more preferable. Two or more of these may be blended. “/” Represents a copolymer and the same applies hereinafter.

  The relative viscosity (ηr) of the (A-1) semi-aromatic polyamide resin in the present invention is preferably 2.0 or more and 2.8 or less. (A-1) If the relative viscosity of the semi-aromatic polyamide resin is 2.0 or more, the mechanical properties of the molded product can be further improved. 2.05 or more is more preferable, and 2.1 or more is more preferable. On the other hand, if the relative viscosity of the (A-1) semi-aromatic polyamide resin is 2.8 or less, the moldability of the resin composition can be improved. 2.7 or less is more preferable, and 2.6 or less is more preferable. In addition, the relative viscosity of (A-1) semi-aromatic polyamide resin is a value measured at 25 ° C. using an Ostwald viscometer for a 98% sulfuric acid solution having a resin concentration of 0.01 g / ml. (A-1) The relative viscosity of the semi-aromatic polyamide resin depends on, for example, polymerization conditions such as pressure, temperature and polymerization time during production of the semi-aromatic polyamide resin, and raw material compositions such as dicarboxylic acid, diamine and terminal blocker. , Can be adjusted to the desired range. For example, with respect to the polymerization conditions, the higher the degree of vacuum, the higher the relative viscosity, and the longer the polymerization time, the higher the relative viscosity. Moreover, about raw material composition, relative viscosity can be made high, so that the composition of dicarboxylic acid and diamine is brought close to equimolar, and relative viscosity can be made high, so that the amount of terminal blocker compounding amount is reduced.

  The (A-2) polyamide resin in the present invention has a difference between the melting point (Tm) and the temperature-falling crystallization peak temperature (Tc), that is, Tm-Tc is 50 ° C. or higher and lower than 90 ° C. (A-2) When the Tm-Tc of the polyamide resin is less than 50 ° C., the surface roughness of the molded article increases, and the surface appearance decreases. From the viewpoint of further reducing the surface roughness of the molded article, Tm-Tc of the (A-2) polyamide resin is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher. On the other hand, when the Tm-Tc of the (A-2) polyamide resin is 90 ° C. or higher, waviness-like irregularities (surface waviness) on the surface of the molded article increase, and the surface appearance deteriorates. From the viewpoint of further reducing the surface waviness of the molded product, Tm-Tc of the (A-2) polyamide resin is preferably less than 85 ° C, and more preferably less than 80 ° C.

  Here, the melting point (Tm) of the polyamide resin (A-2) in the present invention refers to the temperature at the top of the melting endothermic peak, and (A-2) the polyamide resin 30 ° C. according to JIS K7121 (1987). Means a melting endothermic peak temperature in a DSC curve when the amount of heat is measured by raising the temperature at a rate of 10 ° C./min. For the measurement of the melting point, a differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used. When two or more melting endothermic peaks are observed, the melting endothermic peak temperature existing on the higher temperature side is defined as Tm. Tm is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 220 ° C. or higher from the viewpoint of heat resistance. On the other hand, from the viewpoint of suppressing decomposition during melt molding, it is preferably 320 ° C. or lower, more preferably 300 ° C. or lower, and even more preferably 280 ° C. or lower.

  On the other hand, the temperature drop crystallization peak temperature (Tc) of the (A-2) polyamide resin in the present invention refers to the temperature at the top of the crystallization exothermic peak, and according to JIS K7121 (1987), (A-2) The polyamide resin is heated from 30 ° C. at a rate of 10 ° C./min to a temperature 30 ° C. higher than the end temperature of the melting endothermic peak, and further maintained at this temperature for 10 minutes, and then the temperature is lowered at a rate of 10 ° C./min. It means the temperature at the top of the crystallization exothermic peak in the DSC curve when measured. A differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used to measure the temperature-falling crystallization peak temperature. When two or more cooling crystallization peaks are observed, the crystallization exothermic peak temperature existing on the higher temperature side is defined as Tc. Tc is not particularly limited as long as the difference from Tm is 50 ° C. or higher and lower than 90 ° C., but is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, from the viewpoint of further reducing the surface roughness of the molded product. More preferably, it is not lower than ° C. On the other hand, from the viewpoint of further reducing the surface waviness of the molded product, 260 ° C. or lower is preferable, 240 ° C. or lower is more preferable, and 220 ° C. or lower is further preferable.

  Examples of polyamide resins having a Tm-Tc of 50 ° C. or higher and lower than 90 ° C. include polyamide 6, polyamide 46, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/66 / 6I, polyamide 6/612, polyamide MXD (m-xylylenediamine) 6 and the like. Two or more of these may be blended.

  Further, the heat of fusion (ΔHm) of the (A-2) polyamide resin in the present invention is preferably 50 J / g or less, and the surface waviness of the molded product can be further reduced. From the viewpoint of further reducing the surface waviness of the molded product, ΔHm of the (A-2) polyamide resin is more preferably 45 J / g or less, and further preferably 40 J / g or less. On the other hand, from the viewpoint of further improving the mechanical properties of the molded product, 10 J / g or more is preferable, 15 J / g or more is more preferable, and 20 J / g or more is more preferable.

  Here, the heat of fusion (ΔHm) of the (A-2) polyamide resin in the present invention is (A-2) the polyamide resin at a rate of 30 ° C. to 10 ° C./min according to JIS K7122 (1987). It means the melting endotherm in the DSC curve when the temperature is measured by raising the temperature. For the measurement of the heat of fusion, a differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used.

  The relative viscosity (ηr) of the (A-2) polyamide resin in the present invention is preferably 1.8 or more and 4.0 or less. (A-2) If the relative viscosity of the polyamide resin is 1.8 or more, the mechanical properties of the molded product can be further improved. 1.9 or more is more preferable, and 2.0 or more is more preferable. On the other hand, if the relative viscosity of the (A-2) polyamide resin is 4.0 or less, the moldability of the resin composition can be improved. 3.5 or less is more preferable, 3.0 or less is more preferable, and 2.8 or less is more preferable. The relative viscosity of the (A-2) polyamide resin is a value measured with an Ostwald viscometer at 25 ° C. with respect to a 98% sulfuric acid solution having a resin concentration of 0.01 g / ml. (A-2) The relative viscosity of the polyamide resin depends on, for example, the polymerization conditions such as pressure, temperature, and polymerization time during the production of the semi-aromatic polyamide resin, and the raw material composition such as dicarboxylic acid, diamine, and end-capping agent. Can be adjusted to the range. For example, with respect to the polymerization conditions, the higher the degree of vacuum, the higher the relative viscosity, and the longer the polymerization time, the higher the relative viscosity. Moreover, about raw material composition, relative viscosity can be made high, so that the composition of dicarboxylic acid and diamine is brought close to equimolar, and relative viscosity can be made high, so that the amount of terminal blocker compounding amount is reduced.

  (A-1) Semi-aromatic polyamide resin and (A-2) Polyamide resin can be produced by, for example, heating diamine and dicarboxylic acid or a salt thereof as raw materials to obtain a low-order condensate, Examples thereof include a method of increasing the degree of polymerization by phase polymerization and / or melt polymerization. Two-stage polymerization in which the low-order condensate is once taken out and solid-phase polymerization and / or melt polymerization is performed. Following the production process of the low-order condensate, solid-phase polymerization and / or melt polymerization is performed in the same reaction vessel. Either of these may be used. Solid phase polymerization refers to a step of heating in a temperature range of 100 ° C. or higher and lower than the melting point under reduced pressure or in an inert gas, and melt polymerization refers to a step of heating to a melting point or higher under normal pressure or reduced pressure. Point to.

  The blending amount of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin in the carbon fiber reinforced polyamide resin composition of the present invention is (A-1) semi-aromatic polyamide resin and (A-2). (A-1) The semi-aromatic polyamide resin is 50 parts by weight or more and 99 parts by weight or less, and (A-2) The polyamide resin is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total polyamide resin. When (A-1) a semi-aromatic polyamide resin is blended in an amount of less than 50 parts by weight and (A-2) a polyamide resin is blended in an amount of more than 50 parts by weight, the water absorption and surface waviness of the molded product increase. It is preferable to blend 55 parts by weight or more of (A-1) semi-aromatic polyamide resin and 45 parts by weight or less of (A-2) polyamide resin, and (A-1) 60 parts by weight or more of semi-aromatic polyamide resin, More preferably, (A-2) 40 parts by weight or less of the polyamide resin is blended, (A-1) 65 parts by weight or more of the semi-aromatic polyamide resin, and (A-2) 35 parts by weight or less of the polyamide resin. Is more preferable. On the other hand, when (A-1) the semi-aromatic polyamide resin exceeds 99 parts by weight and (A-2) the polyamide resin is less than 1 part by weight, the surface roughness of the molded article increases. (A-1) 95 parts by weight or less of semi-aromatic polyamide resin, (A-2) 5 parts by weight or more of polyamide resin is preferably blended, (A-1) 90 parts by weight or less of semi-aromatic polyamide resin, It is more preferable to blend 10 parts by weight or more of (A-2) polyamide resin, (A-1) 85 parts by weight or less of semi-aromatic polyamide resin, and (A-2) 15 parts by weight or more of polyamide resin. Is more preferable.

  Examples of (B) carbon fibers in the present invention include carbonaceous fibers and graphite fibers produced using polyacrylonitrile (PAN), pitch, rayon, lignin, hydrocarbon gas, and the like. Two or more of these may be blended. Among these, PAN-based carbon fibers are preferable because they are more excellent in improving mechanical properties. (B) Carbon fiber may be coat | covered with metals, such as nickel, copper, and ytterbium.

  (B) As a shape of carbon fiber, a chopped strand, a roving strand, a milled fiber, etc. are common. (B) The diameter of the carbon fiber is generally 15 μm or less, preferably 5 to 10 μm.

  (B) Although the form of carbon fiber is not particularly limited, a carbon fiber bundle composed of several thousand to several hundred thousand carbon fibers or a milled form obtained by pulverizing the carbon fiber bundle is preferable. Examples of the carbon fiber bundle include those obtained by a roving method using directly continuous fibers, and chopped strands cut to a predetermined length. Among these, chopped strands are preferable. The number of filaments of the carbon fiber strand that is the precursor of the chopped carbon fiber is preferably 1,000 to 150,000, which can reduce the manufacturing cost and improve the stability in the production process.

  In the present invention, the strand elastic modulus of (B) carbon fiber is preferably 150 GPa or more, more preferably 220 GPa or more, from the viewpoint of further improving the mechanical properties of the molded product. On the other hand, the strand elastic modulus is preferably 1000 GPa or less, more preferably 500 GPa or less, from the viewpoint of further improving the moldability.

  The strand strength of the (B) carbon fiber in the present invention is preferably 1 GPa or more, more preferably 3 GPa or more, from the viewpoint of further improving the mechanical properties of the molded product. On the other hand, the strand strength is preferably 10 GPa or less and more preferably 5 GPa or less from the viewpoint of further reducing the surface waviness of the molded product.

  Here, the strand elastic modulus and strand strength refer to the elastic modulus and strength of a strand produced by impregnating and curing an epoxy resin to a continuous fiber bundle composed of 1,000 to 150,000 carbon fiber single fibers. This is a value obtained by subjecting the test piece to a tensile test according to JIS R 7601 (1986).

  The carbon fiber (B) in the present invention may be subjected to surface oxidation treatment, and can improve the adhesion with the (A-1) semi-aromatic polyamide resin or the (A-2) polyamide resin. Examples of the surface oxidation treatment include surface oxidation treatment by energization treatment, oxidation treatment in an oxidizing gas atmosphere such as ozone, and the like.

  Further, (B) the carbon fiber may have a coupling agent, a sizing agent or the like attached to the surface thereof, and (A-1) wetness with respect to the semi-aromatic polyamide resin or (A-2) polyamide resin. And (B) the handling property of the carbon fiber can be improved. Examples of the coupling agent include amino, epoxy, chloro, mercapto, and cationic silane coupling agents, and examples include amino silane coupling agents. Two or more of these may be used. Examples of the sizing agent include maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, and the like. Two or more of these may be used. Among these, a sizing agent containing a urethane compound or an epoxy compound is preferable.

  (B) When carbon fiber has a coupling agent or sizing agent attached to the surface thereof, the content of the coupling agent and sizing agent is (A-1) semi-aromatic polyamide resin or (A-2). ) From the viewpoint of further improving the wettability with respect to the polyamide resin, the content is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more in the (B) carbon fiber containing a coupling agent and a sizing agent. On the other hand, from the viewpoint of further improving the handleability of (B) carbon fiber, it is preferably 10% by weight or less, and more preferably 6% by weight or less.

  Moreover, the (B) carbon fiber in this invention may be provided with a sizing agent. Examples of a method for producing a chopped carbon fiber by applying a sizing agent to a strand of carbon fiber include, for example, the method described in Japanese Patent Publication No. 62-9541 and the glass fiber chopped strand, Japanese Patent Application Laid-Open No. Sho 62-244606, Examples include the method described in JP-A-5-261729.

  The blending amount of (B) carbon fiber in the carbon fiber reinforced polyamide resin composition of the present invention is 10 weights with respect to a total of 100 parts by weight of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin. Part to 100 parts by weight. (B) When the compounding amount of the carbon fiber is less than 10 parts by weight, the mechanical properties of the molded product are deteriorated. 15 parts by weight or more is preferable, and 20 parts by weight or more is more preferable. On the other hand, when the blending amount of (B) carbon fiber exceeds 100 parts by weight, the productivity and molding processability of the resin composition and the mechanical properties of the molded product are lowered, and the surface waviness, surface roughness and warpage of the molded product are reduced. Increase. 80 parts by weight or less is preferable, 70 parts by weight or less is more preferable, and 60 parts by weight or less is more preferable.

  Moreover, the compounding ratio ((A-2) / (B)) of (A-2) polyamide resin and (B) carbon fiber in the carbon fiber reinforced polyamide resin composition of the present invention is 0.15 or more and 2.50 or less. In this range, a molded product having an excellent balance of water absorption, mechanical properties and surface appearance can be obtained. When the blending ratio of (A-2) / (B) is 0.15 or more, improvement of mechanical properties, surface roughness, and warpage can be further reduced. 0.20 or more is more preferable, 0.25 or more is more preferable, and 0.30 or more is most preferable. On the other hand, if the blending ratio of (A-2) / (B) is 2.50 or less, water absorption and surface waviness can be further reduced. 2.00 or less is more preferable, 1.50 or less is more preferable, and 1.00 or less is most preferable.

  In the carbon fiber reinforced polyamide resin composition of the present invention, (C) a polyvalent amine compound having 3 or more amino groups in one molecule (hereinafter referred to as “(C) polyvalent amine compound” may be described. May be added, and the mechanical properties and moldability can be further improved. Moreover, since the mold transferability is excellent, the surface roughness of the molded product can be further reduced. (C) The polyvalent amine compound may be a low molecular compound or a polymer.

  As the polyvalent amine compound (C) in the present invention, an aliphatic compound having 3 or more amino groups in one molecule is preferable. Aliphatic compounds having three or more amino groups in one molecule are compatible with (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin and (B) interfacial adhesion with carbon fiber. Therefore, the mechanical properties and surface appearance of the molded product can be further improved. The number of amino groups in one molecule is preferably 4 or more, and more preferably 6 or more.

  In the case of a low-molecular compound, the number of amino groups in one molecule can be calculated by specifying the structural formula of the compound by a normal analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). it can. In the case of a polymer, the ratio of the monomer containing the amino group contained in the polymer is a weight%, the number average molecular weight of the polymer is b, and the gram equivalent of the monomer containing the amino group (molecular weight of monomer / amino group) When the valence of) is c, the average number of amino groups can be calculated as (a / 100) × b / c.

  (C) Examples of the polyvalent amine compound include 3 amino groups such as 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane and the like. Amino groups such as 1,2,2,3-tetraaminopropane, 1,2,3-triamino-2-methylaminopropane, 1,2,3,4-tetraaminobutane and isomers thereof Compounds having four amino acids, compounds having five amino groups such as 3,6,9-triazaundecane-1,11-diamine, and 3,6,9,12-tetraazatetradecane-1,14-diamine 1,1,2,2,3,3-hexaaminopropane, 1,1,2,3,3-pentaamino-2methylaminopropane, 1,1,2,2,3,4-hexaaminobutane And their opposite sex And an amino group of a compound having six such, such as polyethyleneimine obtained by polymerizing ethylene imine.

  The molecular weight of the (C) polyvalent amine compound in the present invention is preferably 50 to 10,000. (C) If the molecular weight of the polyvalent amine compound is 50 or more, it is excellent in workability because it is difficult to volatilize during melt-kneading. (C) The molecular weight of the polyvalent amine compound is preferably 150 or more, and more preferably 200 or more. On the other hand, if the molecular weight of the (C) polyvalent amine compound is 10,000 or less, the compatibility with the (A-1) semi-aromatic polyamide resin and (A-2) the polyamide resin becomes higher, and thus the effect of the present invention. Is played more prominently. (C) The molecular weight of the polyvalent amine compound is preferably 6000 or less, more preferably 4000 or less, and even more preferably 1000 or less.

  (C) In the case of a low molecular weight compound, the molecular weight of the polyvalent amine compound should be calculated by specifying the structural formula of the compound by an ordinary analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). Can do. In the case of a polymer, the molecular weight is the weight average molecular weight (Mw) calculated using gel permeation chromatography (GPC). The weight average molecular weight is determined when the solvent in which the compound is dissolved, for example, hexafluoroisopropanol is used as the mobile phase, polymethyl methacrylate (PMMA) is used as the standard substance, and the column is matched to the solvent. For example, when using hexafluoroisopropanol, Shimadzu It can measure using a differential refractometer as a detector using "shodex GPC HPIP-806M" by GL Corporation.

  The blending amount of the (C) polyvalent amine compound in the carbon fiber reinforced polyamide resin composition of the present invention is based on a total of 100 parts by weight of the (A-1) semi-aromatic polyamide resin and the (A-2) polyamide resin. The amount is preferably 0.1 part by weight or more and 5 parts by weight or less. (C) By mix | blending 0.1 weight part or more of polyvalent amine compounds, a mechanical characteristic can be improved more and surface waviness can be reduced more. 0.2 parts by weight or more is more preferable, and 0.5 parts by weight or more is more preferable. On the other hand, the water absorption can be further reduced by blending 5 parts by weight or less of the (C) polyvalent amine compound. 4.0 parts by weight or less is more preferable, and 3.0 parts by weight or less is more preferable.

  The carbon fiber reinforced polyamide resin composition of the present invention includes a stabilizer, a mold release agent, an ultraviolet absorber, a colorant, a flame retardant, a flame retardant aid, an anti-dripping agent, and a lubricant as long as the effects of the present invention are not impaired. , Fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, flow modifiers, impact modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, and other additives (B) Fillers other than carbon fibers, (A-1) semi-aromatic polyamide resins, and (A-2) thermoplastic resins and thermosetting resins other than polyamide resins can be blended. These blending amounts are preferably 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight in total of the (A-1) semi-aromatic polyamide resin and the (A-2) polyamide resin. By blending 0.01 part by weight or more, the desired characteristics can be expressed. 0.05 parts by weight or more is more preferable, and 0.1 parts by weight or more is more preferable. On the other hand, by blending 10 parts by weight or less, low water absorption, mechanical properties and surface appearance, which are the effects of the present invention, are not impaired. 5 parts by weight or less is more preferable, and 3 parts by weight or less is more preferable.

In the carbon fiber reinforced polyamide resin composition of the present invention, the amino terminal group concentration of the carbon fiber reinforced polyamide resin composition is 3 × 10 with respect to the total of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin. ^It is preferably from ⁻⁵ eq / g to 20 × 10 ⁻⁵ eq / g. By setting the amino end group concentration to 3 × 10 ⁻⁵ eq / g or more, the interfacial adhesion between (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin and (B) carbon fiber is improved. The mechanical properties and surface appearance of the molded product can be further improved. In addition, the adhesion with different materials can be improved. Amino end group concentration is more preferably not less than 5 × ¹⁰ -5 eq / g, still more preferably at least ¹⁰ × 10 -5 eq / g. On the other hand, by setting the amino end group concentration to 20 × 10 ⁻⁵ eq / g or less, decomposition and gas generation at the time of residence can be reduced, and surface appearance deterioration can be suppressed. The amino end group concentration is more preferably 18 × 10 ⁻⁵ eq / g or less, and further preferably 15 × 10 ⁻⁵ eq / g or less.

Here, in the carbon fiber reinforced polyamide resin composition of the present invention, the amino terminal group concentration of the carbon fiber reinforced polyamide resin composition with respect to the total of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin is It can be obtained by the following method. First, after the carbon fiber reinforced polyamide resin composition is vacuum-dried, about 0.5 g is precisely weighed and dissolved in 25 ml of a phenol / ethanol mixed solution at room temperature. By titrating the solution using a hydrochloric acid / ethanol solution as a titrant and a thymol blue solution as an indicator, the amino end group concentration [NH ₂ ] is determined. The amino end group concentration [NH ₂ ] is calculated using the following formula.
Amino end group concentration [NH ₂ ] = (A−B) × f × N × 10 ⁻³ / (W × c × 10 ⁻² )
A: Titration volume of 1 / 50N-HCL (ml)
B: Titration volume of 1 / 50N-HCL required for blank (ml)
f: 1/50 N-HCL titer N: 1/50
W: Sampling weight (g)
c: Total concentration (% by weight) of (A-1) and (A-2) in the composition.

  In the carbon fiber reinforced polyamide resin composition of the present invention, as means for setting the amino terminal group concentration relative to the total of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin, for example, carbon fiber A method of modifying the terminal of the polyamide resin by blending an end-blocking agent and the (C) polyvalent amine compound during the production of the reinforced polyamide resin composition, (A-1) a semi-aromatic polyamide resin, and (A-2) Examples thereof include polymerization conditions such as pressure, temperature and polymerization time during the production of polyamide resin, and methods for adjusting raw material compositions such as dicarboxylic acid, diamine and terminal blocker.

  The carbon fiber reinforced polyamide resin composition of the present invention preferably has a temperature-falling crystallization peak temperature (Tc) in each of a range of 220 ° C. or higher and lower than 300 ° C. and a range of 160 ° C. or higher and lower than 220 ° C. Roughness, surface waviness and warpage can be further reduced. Since a component having a temperature-falling crystallization peak temperature (Tc) in the range of 220 ° C. or more and less than 300 ° C. is crystallized early during molding, shrinkage in the thickness direction can be suppressed and surface waviness can be further reduced. On the other hand, since the component having the temperature-falling crystallization peak temperature (Tc) in the range of 160 ° C. or higher and lower than 220 ° C. is slowly solidified to improve the mold transferability, the surface roughness can be reduced. Furthermore, the presence of a part of the components each having a temperature-falling crystallization peak in such a range is present in a compatible state, so that the orientation of crystals generated with a time difference can be relaxed, and warping during molding can be further reduced.

  Tc of 220 ° C. or more and less than 300 ° C. is derived from (A-1) a semi-aromatic polyamide resin. When Tc derived from (A-1) is 220 ° C. or higher, the surface waviness of the molded product can be further reduced. Tc is more preferably 225 ° C. or higher, and more preferably 230 ° C. or higher. On the other hand, if Tc derived from (A-1) is less than 300 ° C., the surface roughness of the molded product can be further improved. Tc is more preferably 280 ° C. or less, and further preferably 260 ° C. or less. Moreover, Tc in the range of 160 ° C. or higher and lower than 220 ° C. is derived from (A-2) polyamide resin. When the Tc derived from (A-2) is 160 ° C. or higher, the surface roughness of the molded product can be further improved. Tc is more preferably 170 ° C. or higher, and further preferably 180 ° C. or higher. On the other hand, if Tc derived from (A-2) is less than 220 ° C., the surface waviness of the molded product can be further reduced. Tc is more preferably less than 215 ° C and even more preferably less than 210 ° C.

  Here, the temperature-falling crystallization peak temperature (Tc) of the carbon fiber reinforced polyamide resin composition in the present invention refers to the temperature at the top of the crystallization exothermic peak as the carbon fiber reinforced polyamide resin composition, and JIS K7121 (1987). ), The carbon fiber reinforced polyamide resin composition is heated to a temperature 30 ° C. higher than the melting endothermic peak end temperature, and further maintained at this temperature for 10 minutes, and then the temperature is decreased at a rate of 10 ° C./min. It means the temperature at the top of the crystallization exothermic peak in the DSC curve when measured. A differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used to measure the temperature-falling crystallization peak temperature.

  Examples of means for setting the temperature-falling crystallization peak temperature (Tc) of the carbon fiber reinforced polyamide resin composition in the present invention to such a range include, for example, the aforementioned (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin. And the like, and a method of obtaining a carbon fiber reinforced polyamide resin composition by a preferable production method described later.

  The carbon fiber reinforced polyamide resin composition of the present invention preferably has a semi-crystallization time in the range of 5 seconds or more and 60 seconds or less. By making such a range, solidification during molding is delayed and mold transferability is improved. Further, by suppressing the residual strain due to rapid crystallization, surface roughness and warpage can be further reduced. Furthermore, it can be expected to suppress the appearance and strength reduction of the weld portion that occurs in thin and complex shapes. On the other hand, by setting it as such a range, crystallization can sufficiently proceed within the cooling and solidifying time in the mold, and thus excellent mechanical properties can be expressed. If the half crystallization time is 5 seconds or more, the surface roughness and warpage of the molded product can be further reduced. The half crystallization time is more preferably 10 seconds or more, and further preferably 15 seconds or more. On the other hand, if the half crystallization time is 60 seconds or less, the mechanical properties of the molded product can be further improved. The half crystallization time is more preferably 50 seconds or less, and further preferably 40 seconds or less.

  Here, the semi-crystallization time of the carbon fiber reinforced polyamide resin composition in the present invention is a temperature that is 30 ° C. higher than the endothermic peak end temperature of the carbon fiber reinforced polyamide resin composition at a rate of 30 ° C. to 10 ° C./min. The temperature is further maintained at this temperature for 10 minutes, and then rapidly cooled to an arbitrary temperature between (A-1) the glass transition temperature (Tg) of the semi-aromatic polyamide resin and Tg + 60 ° C. at a rate of 500 ° C./min. Keep isothermal. In the DSC curve in which the amount of heat at this time is measured, it means the elapsed time corresponding to half the calorific value of the total crystallization calorific value. The isothermal holding temperature is preferably measured from (A-1) the glass transition temperature (Tg) of the semi-aromatic polyamide resin to Tg + 60 ° C. from the point of reflecting crystallinity at the time of molding. If it is more than a glass transition temperature (Tg), a mechanical characteristic can be improved more by the crystallization promotion of a molded article. The isothermal holding temperature is more preferably Tg + 10 ° C. or higher, and further preferably Tg + 20 ° C. or higher. On the other hand, if the isothermal holding temperature is Tg + 60 ° C. or less, productivity can be further improved by shortening the cooling and solidifying time of the molded product. The isothermal holding temperature is more preferably Tg + 50 ° C. or less, and further preferably Tg + 40 ° C. or less. For the measurement of the half crystallization time, a differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used.

  Examples of means for setting the semi-crystallization time of the carbon fiber reinforced polyamide resin composition in the present invention to such a range include the above-mentioned (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin described above. A method of combining at a preferred blending ratio, a method of combining (A-2) a polyamide resin and (B) carbon fiber at a preferred blending ratio described above, and a method of obtaining a carbon fiber reinforced polyamide resin composition by a preferred production method described below. Etc.

  The glass transition temperature (Tg) of the (A-1) semi-aromatic polyamide resin is (A-1) from 30 ° C. to 10 ° C./min in accordance with JIS K7121 (1987). It can be obtained from the baseline shift in the DSC curve by measuring the amount of heat by heating at a rate. For the measurement of the glass transition temperature (Tg), a differential scanning calorimeter, for example, EXSTAR DSC6000 manufactured by Seiko Instruments Inc. can be used.

  The carbon fiber reinforced polyamide resin composition of the present invention is, for example, (A-1) semi-aromatic with respect to a total of 100 parts by weight of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin. Manufactured by blending 50 parts by weight to 99 parts by weight of polyamide resin, (A-2) 1 part by weight to 50 parts by weight of polyamide resin, and (B) 10 parts by weight to 100 parts by weight of carbon fiber. Can do. These are preferably melt kneaded.

  (A-1) As a semi-aromatic polyamide resin, (A-2) polyamide resin, (B) carbon fiber and (C) a polyvalent amine compound and other additives as needed, as a melt-kneading apparatus, Examples thereof include an extruder and a continuous kneader that can be used for resin processing, which can be melted and kneaded under moderate shearing conditions. For example, a single screw extruder or kneader with one screw, a twin screw extruder or kneader with two screws, a multi-screw extruder or kneader with three or more screws, a tandem extruder that combines an extruder and a kneader, etc. Is mentioned. A twin screw extruder capable of continuous melt kneading is preferred. These may be provided with side feeders that can only supply raw materials without being melt-kneaded. As a screw element design of the melt-kneading apparatus, a melting or non-melting conveyance zone having a full flight screw, a sealing zone having a seal ring or the like, a mixing zone having unimelt, kneading, or the like can be combined. It is preferable to have two or more seal zones and / or mixing zones and two or more raw material supply ports.

  For example, when melt-kneading using a twin screw extruder, the barrel set temperature is a temperature range in which (A-1) the semi-aromatic polyamide resin and (A-2) the polyamide resin are melted and decomposition of the resin is suppressed. It is preferable that Specifically, melt kneading is preferably performed at one of the higher melting point of (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin, at a barrel setting temperature of 10 ° C. or higher and 360 ° C. or lower. As the barrel set temperature becomes higher in the above range, the affinity between (A-1) the semi-aromatic polyamide resin and (A-2) the polyamide resin and (B) the dispersibility of the carbon fibers are further improved. In addition, (A-1) a semi-aromatic polyamide resin, (A-2) a polyamide resin and, if necessary, (C) a polyvalent amine compound and other additives are mainly located upstream of the twin-screw extruder. It is preferable to supply from a raw material supply port, and it is preferable to supply (B) carbon fiber from the supply port located between the main raw material supply port and the discharge port located downstream. (B) By adjusting the supply position of carbon fiber, the fiber length of (B) carbon fiber in the carbon fiber reinforced polyamide resin composition can be easily adjusted to a desired range. Specifically, in the case of a screw design having two or more seal zones and / or mixing zones, the seal zone and / or mixing zone closest to the main material supply port and the seal zone and / or mixing zone closest to the discharge port And an intermediate position is preferred.

When (A-1) semi-aromatic polyamide resin, (A-2) polyamide resin, (B) carbon fiber and (C) polyvalent amine compound and other additives as required are melt-kneaded, the following formula is used. The total shearing amount is preferably in the range of 200 to 2000.
Total shear amount = shear rate (γ) × dwell time (t)
Shear rate = (D × π × N) / H
Residence time = (W x H x L) / Q
D: Screw diameter (cm)
N: Screw rotation speed (rps)
H: Screw groove depth (cm)
W: Screw groove width (pitch) (cm)
L: Screw length (cm)
Q: Supply amount (g / s)

  The carbon fiber reinforced polyamide resin composition of the present invention has a total crystallization amount falling within such a range, and the temperature-falling crystallization peak temperature in each of the above-described range of 220 ° C. or more and less than 300 ° C. and the range of 160 ° C. or more and less than 220 ° C. The resin composition having (Tc) is more likely to obtain a resin composition having the above-described half-crystallization time in the range of 5 seconds to 60 seconds.

  When the total shearing amount is 200 or more, the affinity between (A-1) the semi-aromatic polyamide resin and (A-2) the polyamide resin and (B) the dispersibility of the carbon fibers are further improved. The total shear amount is more preferably 300 or more, and further preferably 400 or more. On the other hand, if the total shearing amount is 2000 or less, deterioration of (A-1) semi-aromatic polyamide resin, (A-2) polyamide resin and (B) breakage of carbon fibers can be further suppressed. The total shear amount is more preferably 1800 or less, and further preferably 1500 or less.

  The carbon fiber reinforced polyamide resin composition of the present invention is preferably molded after being pelletized. The weight average fiber length of the (B) carbon fiber in the pellet is preferably 0.10 mm or more, more preferably 0.15 mm or more, and further preferably 0.20 mm or more from the viewpoint of further improving the mechanical properties of the molded product. On the other hand, 2 mm or less is preferable, 1.5 mm or less is more preferable, and 1.0 mm or less is more preferable from the viewpoint of further improving the surface appearance of the pellets and molded products. Further, the number average fiber length of the (B) carbon fiber in the pellet is preferably 0.10 mm or more, more preferably 0.15 mm or more, and further preferably 0.20 mm or more from the viewpoint of further improving the mechanical properties of the molded product. preferable. On the other hand, 2 mm or less is preferable, 1.5 mm or less is more preferable, and 1.0 mm or less is more preferable from the viewpoint of further improving the surface appearance of the pellets and molded products.

Here, the weight average fiber length and the number average fiber length of the carbon fibers in the pellet are determined by baking the pellet at 500 ° C. for 1 hour, dispersing the obtained ash in water, filtering, and then removing the residue with an optical microscope. It can be converted from the fiber length measured for 1,000 fibers. Specifically, about 10 g of carbon fiber reinforced polyamide resin composition pellets are placed in a crucible, steamed until no flammable gas is generated on an electric stove, and then further 1 hour in an electric furnace set at 500 ° C. Only the carbon fiber residue is obtained by firing. Observe an image of the residue magnified 50 to 100 times with an optical microscope, measure the length of 1,000 randomly selected, and use the measured value (mm) (2 decimal places are significant figures) A weight average fiber length (Lw) and a number average fiber length (Ln) are calculated.
Number average fiber length (Ln) = Σ (Li × ni) / Σni
Weight average fiber length (Lw) = Σ (Wi × Li) / ΣWi
= Σ (πri ² × Li × ρ × ni × Li) / Σ (πri ² × Li × ρ × ni)
When the fiber diameter ri and the density ρ are constant, the above expression is simplified and becomes the following expression.
Weight average fiber length (Lw) = Σ (Li ² × ni) / Σ (Li × ni)
Li: Fiber length of carbon fiber ni: Number of carbon fibers of fiber length Li Wi: Weight of carbon fiber ri: Fiber diameter of carbon fiber ρ: Density of carbon fiber.

  Various molded articles can be produced by molding the carbon fiber reinforced polyamide resin composition of the present invention. Examples of the molding method of the carbon fiber reinforced polyamide resin composition include melt molding methods such as injection molding, extrusion molding, press molding, vacuum molding, and blow molding, and injection molding is preferred.

  Injection molding methods include injection molding, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by supercritical fluid injection), insert molding, in-mold coating molding, heat insulating mold molding, and rapid molding. Heating / cooling mold molding, two-color molding, sandwich molding, ultra-high speed injection molding, and the like can be mentioned. 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.

  From the viewpoint of further improving the mechanical properties of the molded product, the weight average fiber length of the (B) carbon fiber in the molded product of the present invention is preferably 0.05 mm or more, more preferably 0.10 mm or more, and 0.15 mm or more. Is more preferable. On the other hand, from the viewpoint of further improving the surface appearance, 1.0 mm or less is preferable, 0.50 mm or less is more preferable, and 0.40 mm or less is more preferable. The number average fiber length of the (B) carbon fiber in the molded product is preferably 0.05 mm or more, more preferably 0.10 mm or more, and more preferably 0.15 mm or more from the viewpoint of further improving the mechanical properties of the molded product. Further preferred. On the other hand, from the viewpoint of further improving the surface appearance of the molded product, 1.0 mm or less is preferable, 0.5 mm or less is more preferable, and 0.40 mm or less is more preferable.

  Here, the weight average fiber length and the number average fiber length of the carbon fibers in the molded product are determined by calcining the molded product at 500 ° C. for 1 hour, dispersing the obtained ash in water, filtering, and removing the residue. It can be converted from the fiber length observed with an optical microscope and measured for 1,000 fibers. A specific measuring method is the same as the weight average fiber length and number average fiber length measurement of the carbon fibers in the pellet.

  According to the carbon fiber reinforced polyamide resin composition of the present invention, a molded product having low water absorption and excellent mechanical properties and surface appearance can be obtained.

  The carbon fiber reinforced polyamide resin composition and molded article of the present invention are preferably used for various applications such as electronic parts, electric parts, household goods, office supplies, automobile / vehicle-related parts, building materials, and sports goods.

  Examples of electronic components include connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, It is preferably used for printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, parabolic antennas, computer-related parts, etc. .

  Examples of electrical components include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other pole rods, electrical components, motors Preferred for cases, notebook PC housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, various gears, various cases, cabinets, etc. used.

  Household and office supplies include, for example, audio / video such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio, laser discs (registered trademark), compact discs, DVDs, etc. Equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, housings for electronic devices such as personal computers and laptops, office computer parts, telephone equipment parts, facsimile parts, copier parts, washing It is preferably used for jigs, motor parts, lighters, typewriters, microscopes, binoculars, cameras, watches, etc.

  Automotive / vehicle-related parts include, for example, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel-related, cooling systems, brake systems, wiper systems, exhaust systems, Intake system pipes, hoses and tubes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle Position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, battery peripheral parts, thermostat base for air conditioner, heating hot air fan -Control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, transmission oil pan, window washer nozzle, air conditioner panel switch board , Fuel-related electromagnetic valve coils, wire harness connectors, SMJ connectors, PCB connectors, door grommets connectors, fuse connectors and other connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings , Brake piston, solenoid bobbin, engine oil pan, engine oil filter, ignition Mounting case, torque control lever, safety belt parts, register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, instrument panel, airbag peripheral parts, door pad, pillar, console box , Various motor housings, roof rails, fenders, garnishes, roof panels, hood panels, trunk lids, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, It is preferably used for wipers and the like.

  As a building material, for example, it is preferable for civil engineering building walls, roofs, ceiling material related parts, window material related parts, heat insulation related parts, flooring related parts, seismic isolation / vibration control parts related parts, lifeline related parts, etc. used.

  Examples of sports equipment include golf-related equipment such as golf clubs and shafts, masks such as American football, baseball, and softball, body protection equipment for sports such as helmets, breast pads, elbow pads, knee pads, and bottom materials for sports shoes. Shoes-related products such as fishing rods, fishing lines, fishing gear-related items such as reels, summer sports-related items such as surfing, winter sports-related items such as skis and snowboards, cycle-related items such as bicycle pedals, and other indoor and outdoor sports-related items It is preferably used for articles.

  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.

  First, a method for evaluating the characteristics of the polyamide resin used in each example and comparative example will be described.

[Glass transition temperature (Tg), melting point (Tm) and temperature-falling crystallization peak temperature (Tc) of polyamide resin]
(A-1) A semi-aromatic polyamide resin to be described later is used in a differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Co., Ltd. according to JIS K7121 (1987). The temperature was raised at a rate of minutes and the amount of heat was measured, and the glass transition temperature (Tg) was determined from the baseline shift in the DSC curve.

  A differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Inc. is used for (A-1) semi-aromatic polyamide resin, (A-2) polyamide resin or (A ′) other polyamide resin described later. In accordance with JIS K7121 (1987), the temperature was increased from 30 ° C. at a rate of 10 ° C./min to measure the calorie, and the melting point (Tm) was determined from the melting endothermic peak temperature in the DSC curve.

  In addition, (A-1) semi-aromatic polyamide resin, (A-2) polyamide resin or (A ′) other polyamide resin, which will be described later, is converted into a differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Inc. ) In accordance with JIS K7121 (1987) at a rate of 30 ° C. to a temperature 30 ° C. higher than the endothermic melting end temperature, and further maintained at this temperature for 10 minutes, The temperature was decreased at a rate of 1 minute / minute, the amount of heat was measured, and the temperature-lowering crystallization peak temperature (Tc) was determined from the temperature at the top of the crystallization exothermic peak in the DSC curve.

[Relative viscosity of (A-1) semi-aromatic polyamide resin]
The assumed viscosity was measured at 25 ° C. using an Ostwald viscometer for a solution dissolved in 98% sulfuric acid so that the resin concentration of (A-1) semi-aromatic polyamide resin described later becomes 0.01 g / ml.

[Amount of heat of fusion of polyamide resin (ΔHm)]
According to JIS K7122 (1987), (A-2) polyamide resin or (A ′) other polyamide resin described later is used with a differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Inc. Then, the temperature was increased from 30 ° C. at a rate of 10 ° C./min, and the amount of heat was measured to determine the heat of fusion (ΔHm).

  Next, the raw material used for the Example and the comparative example is demonstrated.

(A-1) Semi-aromatic polyamide resin (Production Example 1) Production of semi-aromatic polyamide resin (A-1-1) 4539.3 g (27.3 mol) of terephthalic acid, (a) 1,9-nonanediamine (B) 2-methyl-1,8-octanediamine mixture [(a) / (b) = 50/50 (molar ratio)] 4478.8 g (28.3 mol), benzoic acid 101.6 g (0. 83 mol), 9.12 g of sodium hypophosphite monohydrate (0.1% by weight with respect to the total weight of the raw material) and 2.5 liters of water are mixed, charged in a pressure vessel and sealed, and nitrogen is added. Replaced. The mixture was stirred at 100 ° C. for 30 minutes, and then the temperature inside the pressure vessel was raised to 220 ° C. over 2 hours while stirring. At this time, the pressure inside the autoclave increased to 2 MPa. Stirring was continued for 2 hours at 220 ° C., and then the temperature was raised to 230 ° C., and then the reaction was continued for 2 hours while keeping the temperature at 230 ° C., gradually removing water vapor and keeping the pressure at 2 MPa. Next, the pressure was reduced to 1 MPa over 30 minutes, and stirring was further continued at 230 ° C. for 1 hour. Next, the pressure was reduced to normal pressure over 30 minutes, and the contents were discharged into water to obtain a prepolymer.

  The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a particle size of 2 mm or less, and solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 8 hours to obtain all dicarboxylic acids. The unit contains 100 mol% of terephthalic acid-derived units, and contains all diamine units, and contains 1,9-nonanediamine-derived units and 2-methyl-1,8-octanediamine-derived units, 50 mol% each. (A-1-1) semi-aromatic polyamide resin was obtained.

  (A-1-1) The glass transition temperature (Tg) of the semi-aromatic polyamide resin is 119 ° C., the melting point (Tm) is 262 ° C., the temperature-falling crystallization peak temperature (Tc) is 226 ° C., and Tm-Tc is 36 ° C. The relative viscosity was 2.13.

(Production Example 2) Production of semi-aromatic polyamide resin (A-1-2) (a) The molar ratio of a mixture of 1,9-nonanediamine and (b) 2-methyl-1,8-octanediamine is (a). / (B) = In the same manner as in Production Example 1, except for changing to 80/20, 100 mol% of terephthalic acid-derived units are contained in all dicarboxylic acid-derived units, and 1,9 in all diamine-derived units. -A white (A-1-2) semi-aromatic polyamide resin containing 80 mol% of nonanediamine units and 20 mol% of 2-methyl-1,8-octanediamine units was obtained.

  (A-1-2) The semi-aromatic polyamide resin has a glass transition temperature (Tg) of 120 ° C., a melting point (Tm) of 302 ° C., a temperature drop crystallization peak temperature (Tc) of 264 ° C., and a Tm-Tc of 38 ° C. The relative viscosity was 2.15.

(Production Example 3) Production of semi-aromatic polyamide resin (A-1-3) Equal molar amounts of decamethylenediamine and terephthalic acid were mixed so that the total amount was 10 kg, and 0.5 mol relative to the total amount of decamethylenediamine. % Decamethylenediamine was added in excess, and 0.5 parts by weight of benzoic acid and 30 parts by weight of water were further mixed as end-capping agents with respect to a total of 70 parts by weight of these raw materials. And replaced with nitrogen. Then, it was made to react by the method similar to manufacture example 1, and the prepolymer was obtained.

  The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a particle size of 2 mm or less, and solid-phase polymerized at 240 ° C. and 50 Pa for 8 hours to obtain terephthalic acid in all carboxylic acid-derived units. A (A-1-3) semi-aromatic polyamide resin containing 100 mol% of derived units and containing 100 mol% of decamethylenediamine derived units among all diamine derived units was obtained.

  (A-1-3) The glass transition temperature (Tg) of the semi-aromatic polyamide resin is 125 ° C., the melting point (Tm) is 318 ° C., the cooling crystallization peak temperature (Tc) is 281 ° C., and Tm-Tc is 37 ° C. The relative viscosity was 2.30.

(A-2) Polyamide resin (A-2-1) MXD6 resin MX nylon S6001 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used. The melting point (Tm) was 238 ° C., the falling crystallization peak temperature (Tc) was 161 ° C., and Tm-Tc was 77 ° C. The heat of fusion (ΔHm) was 31 J / g.

Production Example 4 Production of Copolymerized Polyamide Resin 76% by weight of equimolar salt of hexamethylenediamine and adipic acid, 16% by weight of equimolar salt of hexamethylenediamine and isophthalic acid, and 8% by weight of ε-caprolactam Into the container, the same amount of pure water as the total amount added was further added, and the pressurized container was sealed and purged with nitrogen. Heating was started while stirring the mixture, and the temperature was raised to the final temperature of 270 ° C. over 2 hours while adjusting the pressure in the pressurized container to 2 MPa. Further, the reaction was allowed to proceed with stirring at 270 ° C. for 2 hours. After gradually removing water vapor over 1 hour, the pressure was lowered to normal pressure, the contents were discharged into a water bath, and pelletized with a strand cutter. A washing treatment of stirring the obtained pellets in 95 ° C. hot water for 5 hours was repeated a total of 4 times to extract and remove unreacted monomers and low polymer. The extracted pellets were dried at 80 ° C. for 50 hours or longer to obtain (A-2-2) terpolymer polyamide resin. The melting point (Tm) was 230 ° C., the cooling crystallization peak temperature (Tc) was 163 ° C., and Tm−Tc was 67 ° C. The heat of fusion (ΔHm) was 44 J / g.

  (A-2-3) Nylon 6 resin was used. The melting point (Tm) was 222 ° C., the temperature-falling crystallization peak temperature (Tc) was 167 ° C., and Tm−Tc was 55 ° C. The heat of fusion (ΔHm) was 60 J / g.

  (A-2-4) Nylon 610 resin was used. The melting point (Tm) was 225 ° C., the temperature-falling crystallization peak temperature (Tc) was 171 ° C., and Tm-Tc was 54 ° C. The heat of fusion (ΔHm) was 56 J / g.

(A ′) Other polyamide resin (A ′) Nylon 12 / MACMI copolymer “Grillamide” (registered trademark) TR55 (manufactured by MMS Japan Co., Ltd.) was used. Neither melting point (Tm) nor cooling crystallization peak temperature (Tc) could be confirmed.

(B) Carbon fiber (B-1) Carbon fiber “Torayca” (registered trademark) cut fiber TV14-006 (manufactured by Toray Industries, Inc.) was used.

(C) Polyvalent amine compound (C-1) Pentaethylenehexamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(D) Other additives (D-1) Sodium hypophosphite (manufactured by Taihei Chemical Industry Co., Ltd.) was used.
(D-2) Chlorine method titanium oxide (rutile type) CR-63 (Ishihara Sangyo Co., Ltd., average particle size 0.21 μm) was used.

[Examples 1 to 19, Comparative Examples 1 to 9]
(A-1) Semi-aromatic polyamide resin, (A-2) Polyamide resin, (A ′) Polyamide resin, (D) Other additives shown in the table are twin screw extruder TEX30α manufactured by Nippon Steel, Ltd. Then, the carbon fiber (B) was fed to a twin screw extruder TEX30α manufactured by Nippon Steel Works using a side feeder and melt kneaded under the extrusion conditions shown in the table. The strand discharged from the die was cooled in water and cut into a length of 3.0 mm by a strand cutter to obtain a carbon fiber reinforced polyamide resin composition pellet. Here, the total shearing amount at the time of melt-kneading was calculated using the following equation.
Total shear amount = shear rate (γ) × dwell time (t)
Shear rate = (D × π × N) / H
Residence time = (W x H x L) / Q
D: Screw diameter (3cm)
N: Screw rotation speed (rps) is described in the table H: Screw groove depth (0.65 cm)
W: Screw groove width (pitch) (2.25 cm)
L: Screw length (105cm)
Q: Supply amount (g / s) is shown in the table

  Various characteristics were evaluated by the following methods using the obtained carbon fiber reinforced polyamide resin composition pellets.

[Amino end group concentration of carbon fiber reinforced polyamide resin composition relative to (A-1) semi-aromatic polyamide resin and (A-2) polyamide resin]
The carbon fiber reinforced polyamide resin composition pellets obtained in each example and comparative example were vacuum-dried at 130 ° C. for 12 hours, and then approximately 0.5 g was precisely weighed, and a phenol / ethanol mixed solution (ratio: 84/16 weight). %) Was dissolved in 25 ml at room temperature. The amino end group concentration [NH ₂ ] was determined by titrating the solution using a hydrochloric acid / ethanol solution as a titrant and a thymol blue solution as an indicator. The amino end group concentration [NH ₂ ] was calculated using the following formula.
Amino end group concentration [NH ₂ ] = (A−B) × f × N × 10 ⁻³ / (W × c × 10 ⁻² )
A: Titration volume of 1 / 50N-HCL (ml)
B: Titration volume of 1 / 50N-HCL required for blank (ml)
f: 1/50 N-HCL titer N: 1/50
W: Sampling weight (g)
c: Total concentration (% by weight) of (A-1) and (A-2) in the composition.

[Cooling crystallization peak temperature of carbon fiber reinforced polyamide resin composition]
The carbon fiber reinforced polyamide resin composition pellets obtained in each example and comparative example were vacuum dried at 140 ° C. for 12 hours, and then used with a differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Inc. In accordance with JIS K7121 (1987), the temperature was increased from 30 ° C. to a temperature 30 ° C. higher than the endothermic melting end temperature at a rate of 10 ° C./min. The temperature was lowered at a rate to measure the amount of heat, and the temperature-falling crystallization peak temperature (Tc) was determined from the temperature at the top of the crystallization exothermic peak in the DSC curve.

[Semi-crystallization time of carbon fiber reinforced polyamide resin composition]
The carbon fiber reinforced polyamide resin composition pellets obtained in each example and comparative example were vacuum dried at 140 ° C. for 12 hours, and then used with a differential scanning calorimeter (Robot DSC, EXSTAR DSC6000 system) manufactured by Seiko Instruments Inc. In accordance with JIS K7121 (1987), the temperature is increased from 30 ° C. to a temperature 30 ° C. higher than the endothermic melting end temperature at a rate of 10 ° C./min. The amount of heat was measured by rapid cooling / isothermal holding at 140 ° C., and the elapsed time corresponding to half the calorific value of the total crystallization calorific value in the DSC curve was determined.

[(B) Fiber length of carbon fiber in molded product]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: ISO 3167 type A test piece was injection molded at a lower limit pressure (minimum filling pressure) +1 MPa. About 10 g was cut out from an ISO 3167 type A test piece, baked in an electric furnace set at 500 ° C. for 1 hour, dispersed in ion-exchanged water, filtered, and the residue was observed with an optical microscope at a magnification of 50 times. However, the length of 1,000 randomly selected samples was measured. From the measured values obtained, the weight average fiber length (Lw) and the number average fiber length (Ln) were calculated according to the following formula.
Number average fiber length (Ln) = Σ (Li × ni) / Σni
Weight average fiber length (Lw) = Σ (Li ² × ni) / Σ (Li × ni)
Li: Fiber length of carbon fiber ni: Number of carbon fibers of fiber length Li.

[Mechanical properties]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: ISO 3167 type A test piece was injection molded at a lower limit pressure (minimum filling pressure) +1 MPa.

  Charpy impact strength (notched) was measured at 23 ° C. in accordance with ISO 179 using a test piece with both sides cut off while leaving the central parallel part of the ISO 3167 type A test piece. The average value of the values measured for 12 test pieces was calculated. Moreover, the bending elastic modulus and bending strength were measured at 23 ° C. according to ISO 178 using an ISO 3167 type A test piece. In any case, the average value of the values measured for six test pieces was calculated. Moreover, the tensile strength was measured at 23 degreeC according to ISO527 using the ISO3167 type A test piece. The average value of the values measured for six test pieces was calculated.

[Water absorption of molded products]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: ISO 3167 type A test piece was injection molded at a lower limit pressure (minimum filling pressure) +1 MPa. After measuring the weight (weight when dried) of ISO 3167 type A test piece, the weight after standing for 500 hours in an environment of 80 ° C. and 95% RH was measured, and the water absorption was calculated from the following formula.
Water absorption (%) = [(weight after 95% RH 500 hours−weight when dried) / weight when dried] × 100.

[Appearance of molded product surface]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: a square plate of 80 mm × 80 mm × 3 mm was injection-molded as a lower limit pressure (minimum filling pressure) +1 MPa.

  Using a square plate of 80 mm x 80 mm x 3 mm, using a surface roughness measuring device (manufactured by ACCRTECH), under the measurement conditions of an evaluation length of 8 mm and a test speed of 0.6 mm / sec, the arithmetic average roughness of the surface of the molded product The thickness (Ra) was measured and the surface roughness was evaluated.

  In addition, using a square plate of 80 mm x 80 mm x 3 mm and using a surface roughness measuring device (manufactured by ACCRTECH), the undulation of the surface of the molded product under the measurement conditions of an evaluation length of 20 mm and a test speed of 0.6 mm / sec. The arithmetic mean height (Wa) value of the curve was measured to evaluate the surface waviness.

[War of molded product]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: A square plate of 80 mm × 80 mm × 1 mm was injection-molded as a lower limit pressure (minimum filling pressure) +1 MPa. One corner of this square plate was fixed with a weight, and the height of the portion with the largest warp height was measured using a height gauge. This was performed for all four corners, and the value with the highest warp height was taken as the warp amount.

[Molding processability]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 140 ° C. for a whole day and night, and then injection speed: 100 mm according to the molding conditions shown in the table using an injection molding machine SG75H-DUZ manufactured by Sumitomo Heavy Industries, Ltd. / Second, injection pressure: Lower limit pressure (minimum filling pressure) + 1 MPa When measuring 80 mm x 80 mm x 3 mm square plate, the lower limit injection pressure for filling the resin into the mold was measured. The smaller this value, the better the moldability.

  The evaluation results of Examples 1 to 19 are shown in Tables 1 and 2, and the evaluation results of Comparative Examples 1 to 9 are shown in Table 3.

  From the comparison between Examples 1 to 19 and Comparative Examples 1 to 9, it can be seen that the carbon fiber reinforced polyamide resin composition of the present invention can provide a molded article having low water absorption and excellent mechanical properties and surface appearance. .

  From the comparison between Examples 3 and 8 and Example 9, it is understood that the surface appearance is better when the (A-2) polyamide resin having a heat of fusion (ΔHm) of 50 J / g or less is used. Further, it is understood from the comparison between Example 3 and Example 15 that the mechanical properties, surface appearance, and molding processability can be further improved by further using (C) a polyvalent amine compound. Further, from comparison between Example 3 and Example 17 and Example 13 and Example 14, carbon having a temperature-decreasing crystallization peak temperature in each of a range of 220 ° C. or higher and lower than 300 ° C. and a range of 160 ° C. or higher and lower than 220 ° C. It can be seen that the mechanical properties and surface appearance can be further improved by the fiber reinforced polyamide resin composition. Further, when Examples 1 and 2 are compared with Examples 3 to 5, the carbon fiber reinforced polyamide resin composition having a semi-crystallization time of 5 to 60 seconds improves surface roughness without deteriorating mechanical properties. It can be seen that the amount of warpage can be suppressed. When Example 17 is compared with Examples 3 to 5, the carbon fiber reinforced polyamide resin composition having a semi-crystallization time of 5 to 60 seconds can improve the surface roughness without deteriorating mechanical properties. I understand.

  The carbon fiber reinforced polyamide resin composition of the present invention is low in water absorption, taking advantage of the properties excellent in mechanical properties and surface appearance, such as automobile parts such as automobile interior parts and automobile exterior parts, sporting goods members, various electric / It can be suitably used for various applications such as electronic component housings, chassis and internal components, and building components.

Claims (8)

(A-1) A semi-aromatic polyamide resin having a difference between the melting point and the cooling crystallization peak temperature of 0 ° C. or more and less than 50 ° C., (A-2) A difference between the melting point and the cooling crystallization peak temperature of 50 ° C. or more and 90 ° C. Less than the polyamide resin and (B) carbon fiber, and a total of 100 parts by weight of (A-1) and (A-2), (A-1) 50 parts by weight or more and 99 parts by weight or less, (A-2) 1 part by weight or more and 50 parts by weight or less, and (B) 10 parts by weight or more and 100 parts by weight or less. 2. The carbon fiber reinforced polyamide resin according to claim 1, wherein the heat difference of fusion (ΔHm) of the polyamide resin having a difference between the melting point and the temperature-falling crystallization peak temperature of 50 ° C. or more and less than 90 ° C. is 50 J / g or less. Composition. The difference between the (A-1) melting point and the cooling crystallization peak temperature is 0 ° C. or more and less than 50 ° C., and the difference between the (A-2) melting point and the cooling crystallization peak temperature is 50 ° C. or more and 90 ° C. (C) 0.1 parts by weight or more and 5 parts by weight or less of a polyvalent amine compound having 3 or more amino groups in one molecule is added to 100 parts by weight of the polyamide resin at a temperature lower than 0 ° C. Item 3. The carbon fiber reinforced polyamide resin composition according to Item 1 or 2. The difference between the (A-1) melting point and the cooling crystallization peak temperature is 0 ° C. or more and less than 50 ° C., and the difference between the (A-2) melting point and the cooling crystallization peak temperature is 50 ° C. or more and 90 ° C. The carbon fiber-reinforced polyamide resin composition according to any one of claims 1 to 3, wherein an amino terminal group concentration of the carbon fiber-reinforced polyamide resin composition with respect to a polyamide resin of less than 0C is 3 x ^10-5 eq / g or more. The carbon fiber reinforced polyamide resin composition according to any one of claims 1 to 4, which has a temperature-falling crystallization peak temperature in each of a range of 220 ° C to less than 300 ° C and a range of 160 ° C to less than 220 ° C. The carbon fiber reinforced polyamide resin composition according to any one of claims 1 to 5, wherein the half crystallization time is 5 seconds or more and 60 seconds or less. (A-1) A semi-aromatic polyamide resin having a difference between the melting point and the cooling crystallization peak temperature of 0 ° C. or more and less than 50 ° C., (A-2) A difference between the melting point and the cooling crystallization peak temperature of 50 ° C. or more and 90 ° C. Less than the polyamide resin and (B) the carbon fiber reinforced polyamide resin composition, wherein (A-) and (A-2) 1) 50 parts by weight or more and 99 parts by weight or less, (A-2) 1 part by weight or more and 50 parts by weight or less, and (B) 10 parts by weight or more and 100 parts by weight or less of a carbon fiber reinforced polyamide resin composition Method. The molded article which consists of a carbon fiber reinforced polyamide resin composition in any one of Claims 1-6.