JP2015224286A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition excellent in die fillability upon molding and capable of obtaining a molding having satisfactory mechanical strength, heat resistance, metal adhesion and chemical resistance.SOLUTION: There is provided a polyamide resin composition having a structural unit including at least a diamine residue and a dicarboxylic acid residue, and the structural unit is blended, to 100 pts.wt. of a polyamide resin (A) including an aliphatic group, an aromatic group and/or an alicyclic group, with a compound (B) including a piperidinyl group, an aromatic group and an amide bond by 0.1-10 pts.wt.

Description

  The present invention relates to a polyamide resin composition and a molded article formed by molding the same.

  Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are therefore preferably used for electrical / electronic component applications, fiber applications, automobile component applications, and the like. For example, it is suitably used for parts such as connectors and breakers for electric / electronic parts, and for automobile engine peripheral parts such as engine covers for automobile parts.

  With respect to the polyamide resin composition used for these applications, for example, a powdery sealing agent containing a copolymerized polyamide resin and a hindered amine light stabilizer (for example, see Patent Document 1) has been proposed. Further, as a light-resistant polyamide fiber structure that prevents discoloration due to heat, etc., a highly light-resistant wholly aromatic polyamide fiber structure comprising a meta-type wholly aromatic polyamide fiber containing a hindered amine antioxidant having a heat-resistant temperature of 145 ° C. or higher. A thing (for example, refer patent document 2) is proposed.

  On the other hand, due to the penetration of surface mounting method (SMT) due to the recent thinning of electric and electronic parts, complicated shape, high density mounting, and efficient soldering process, polyamide resin has higher fluidity and higher Heat resistance is also important. In the automotive field, engine parts have higher heat resistance and chemical resistance due to the increase in the environmental temperature associated with higher output in addition to the modularization of large parts and the reduction in weight of molded parts. It has been demanded.

  In response to such demands, as a polyamide resin composition excellent in fluidity, for example, semi-aromatic polyamide has an amide structure or a urea structure, has a molecular weight in the range of 300 to 3000, Bisphenol is added to a polyamide composition (for example, see Patent Document 3) containing a compound having a midpoint temperature of 350 ° C. or higher in a gravimetric analysis curve and a brominated flame retardant, or a polyamide resin having a melting point of 270 to 340 ° C. A polyamide resin composition containing a fatty acid ester of a similar alkylene oxide adduct and a brominated flame retardant (see, for example, Patent Document 4) has been proposed.

JP 2013-163754 A JP 2003-239136 A JP 2004-107576 A JP 2008-208383 A

  With the recent further reduction in thickness and shape of molded products, polyamide resin compositions are required to have a balance between high fluidity and molding stability during continuous molding (die filling property). In addition, polyamide resin and metal are becoming more complex in electrical and electronic parts and automotive parts, so high metal adhesion due to affinity with the metal surface and conformity to irregularities on the metal surface. It is requested.

  However, although the polyamide resin composition disclosed in Patent Document 1 is excellent in fluidity, the molding stability during continuous molding is insufficient, and the mold filling property, mechanical strength, heat resistance, and chemical resistance are excellent. There was a problem. Further, the polyamide resin composition disclosed in Patent Document 2 uses a high-melting wholly aromatic polyamide, and even when it is a hindered amine antioxidant having a heat resistant temperature of 145 ° C. or higher, it is decomposed during molding processing. There is a problem that molding stability at the time of continuous molding is insufficient and mold filling property, metal adhesion, and chemical resistance are lowered. On the other hand, Patent Documents 3 and 4 propose a resin composition having excellent mechanical strength, heat resistance, and fluidity, but there are problems in molding stability and metal adhesion during continuous molding, and further chemical resistance. Improvements were also sought.

  In view of these problems of the prior art, the present invention is a polyamide resin composition that is excellent in mold filling at the time of molding, and can obtain a molded product having good mechanical strength, heat resistance, metal adhesion, and chemical resistance. It is an issue to provide.

As a result of intensive studies to solve such problems, the present invention has found that the above problems can be solved by a polyamide resin composition containing a compound having a specific structure, and has completed the present invention. That is, the present invention
(1) Polyamide resin (A) 100 having a structural unit containing at least a diamine residue and a dicarboxylic acid residue, and containing an aliphatic group, an aromatic group and / or an alicyclic group in the structural unit A polyamide resin composition comprising 0.1 to 10 parts by weight of a compound (B) containing a piperidinyl group, an aromatic group and an amide bond, relative to parts by weight;
(2) The polyamide resin composition according to (1), wherein the compound (B) has a structure represented by the following general formula (I):

In the general formula (I), R ′ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or —COR ¹ group (R ¹ is hydrogen or an alkyl having 1 to 6 carbon atoms). Group), phenyl group, -COOR ² group (R ² is an alkyl group having 1 to 4 carbon atoms), -NR ³ R ⁴ group (R ³ and R ⁴ may be the same or different, hydrogen, 1 to carbon atoms 12 alkyl groups, cycloalkyl groups having 5 to 6 carbon atoms, phenyl groups, or alkylphenyl groups having 1 to 12 carbon atoms). However, the plurality of R ′ may be the same or different.
(3) The polyamide resin composition according to (1) or (2), wherein the diamine residue in the polyamide resin (A) is an even number of 4 to 18 carbon atoms,
(4) The polyamide resin composition according to any one of (1) to (3), wherein 100 parts by weight of the polyamide resin (A) is further blended with 1 to 200 parts by weight of a filler (C).
(5) A molded product obtained by injection molding the polyamide resin composition according to any one of (1) to (4),
It is.

  The polyamide resin composition of the present invention is excellent in mold filling at the time of molding. The polyamide resin composition of the present invention can provide a molded product having excellent mechanical strength, heat resistance, metal adhesion, and chemical resistance.

  Hereinafter, the present invention will be described in detail. The polyamide resin composition of the present invention has a structural unit containing at least a diamine residue and a dicarboxylic acid residue, and includes an aliphatic group, an aromatic group and / or an alicyclic group in the structural unit. Compound (B) containing piperidinyl group, aromatic group and amide bond with respect to 100 parts by weight of polyamide resin (A) (hereinafter referred to as “polyamide resin (A)”) (hereinafter referred to as “compound (B)”) And 0.1 to 10 parts by weight.

  In the present invention, the polyamide resin (A) has a structural unit containing at least a diamine residue and a dicarboxylic acid residue. By having such a structural unit, the heat resistance of the molded product can be improved. Such a polyamide resin is obtained by polymerizing diamine and dicarboxylic acid. Amino acids and lactams may be further copolymerized with diamine and dicarboxylic acid.

  The polyamide resin (A) has an aliphatic group, an aromatic group and / or an alicyclic group in the structural unit. By having an aliphatic group, the melting point of the polyamide resin (A) can be moderately suppressed, decomposition of the compound (B) during molding processing can be suppressed, and the effect of the compound (B) described later can be enhanced. Moreover, the heat resistance of a molded article can be improved by having an aromatic group and / or an alicyclic group. Furthermore, the mechanical strength and chemical resistance of the molded product can be improved by appropriately increasing the melting point of the polyamide resin, improving the kneadability with the compound (B) described later, and increasing the dispersibility.

  Examples of the diamine constituting the diamine residue include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, Aliphatic diamines such as 2,4- / 2,4,4-trimethylhexamethylenediamine and 5-methylnonamethylenediamine; aromatic diamines such as metaxylylenediamine and paraxylylenediamine; 1,3-bis (amino Methyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4- Aminocyclohexyl Methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and the like alicyclic diamines such as aminoethyl piperazine.

  Examples of the dicarboxylic acid constituting the dicarboxylic acid residue include aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2- Aromatic dicarboxylic acids such as methyl terephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid An acid etc. are mentioned.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.

  Examples of the lactam include ε-caprolactam and ω-laurolactam.

  In the present invention, polyamide homopolymers or copolymers derived from these raw materials containing at least diamine and dicarboxylic acid can be used, and two or more of these may be blended.

  The polyamide resin (A) in the present invention has an aliphatic group in the diamine residue, may have an aromatic group and / or an alicyclic group in the dicarboxylic acid residue, May have an aromatic group and / or an alicyclic group, and may have an aliphatic group in a dicarboxylic acid residue, or an aliphatic group and an aromatic group in a diamine residue or a dicarboxylic acid residue. And / or may have both alicyclic groups. Examples of the combination of raw materials constituting the polyamide resin (A) include, for example, a combination of an aliphatic diamine and an aromatic and / or alicyclic dicarboxylic acid, and an aromatic and / or alicyclic diamine and an aliphatic dicarboxylic acid. Can be mentioned. From the viewpoint of the color tone of the polyamide resin, a combination of an aliphatic diamine and an aromatic and / or alicyclic dicarboxylic acid is preferable.

  The polyamide resin (A) in the present invention has a ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit ({total molecular weight of aromatic group and alicyclic group / molecular weight per structural unit} × 100) is preferably 1 to 40%. Here, the molecular weight per structural unit refers to the molecular weight corresponding to the structural unit constituting the polyamide resin. In the case of a polyamide resin using an amino acid as a raw material, the molecular weight of one water molecule is subtracted from the molecular weight of the amino acid. Equal to the value. In the case of a polyamide resin using lactam as a raw material, it is equal to the molecular weight of lactam. In the case of a polyamide resin using diamine and dicarboxylic acid as raw materials, the value obtained by subtracting the molecular weight of two water molecules from the sum of the molecular weight of dicarboxylic acid and the molecular weight of diamine is equal to 2. On the other hand, the total molecular weight of the aromatic group and alicyclic group refers to the molecular weight corresponding to each structure when it has only the aromatic group or alicyclic group, and has the aromatic group and alicyclic group. Indicates the sum of molecular weights corresponding to each structure. By specifying the structural unit by structural analysis of the polyamide resin (A), the ratio of the total molecular weight of the aromatic group and the alicyclic group to the molecular weight per structural unit can be obtained. In the case of a copolymerized polyamide resin having a plurality of structural units, from the value of the ratio in each structural unit, calculated according to the proportion of each structural unit in the polyamide resin, when using a plurality of polyamide resins in combination, It calculates from the value of the ratio in each polyamide resin according to the blending ratio of the polyamide resin. By setting the ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit to 1% or more, the mechanical strength, heat resistance and chemical resistance of the molded product can be further improved. Moreover, since it is excellent by compatibility with a compound (B), metal mold | die filling property and the metal adhesiveness of a molded article can be improved more. 5% or more is more preferable, 10% or more is more preferable, 15% or more is more preferable, and 18% or more is further more preferable. On the other hand, by setting the ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit to 40% or less, the melting point is moderately suppressed to improve the molding processability, mold filling property, metal adhesion And chemical resistance can be further improved. 35% or less is more preferable, 30% or less is more preferable, and 26% or less is more preferable.

  Specifically, the polyamide resin (A) is polyamide 6 / 6T, polyamide 6 / 6C, polyamide 66 / 6T, polyamide 66 / 6C, polyamide 66 / 6I, polyamide 66 / 6I / 6, polyamide 6T / 6I, polyamide 6T / 12, polyamide 6C / 12, polyamide 66 / 6T / 6I, polyamide MXD6, polyamide MXD10, polyamide PXD6, polyamide PXD10, polyamide 6T / M5T, polyamide 6C / M5C, polyamide 6T / 5T, polyamide 6C / 5C, polyamide 5T / 56, polyamide 5C / 56, polyamide 9T, polyamide 9C, polyamide 9T / M8T, polyamide 9T / M8C, polyamide 10T, polyamide 10T / 66, polyamide 10T / 612, polyamide 12T Coalescence and the like. Two or more of these may be blended.

  The melting point of the polyamide resin (A) is preferably 200 ° C to 330 ° C. By setting the melting point of the polyamide resin (A) to 200 ° C. or higher, the heat resistance can be further improved. In addition, since the melting temperature can be increased, the dispersibility of the compound (B) is excellent, the molding stability during continuous molding can be further improved, and the mechanical strength, metal adhesion and chemical resistance of the molded product can be further improved. it can. 230 degreeC or more is more preferable, 280 degreeC or more is more preferable, and 310 degreeC or more is further more preferable. On the other hand, by setting the melting point of the polyamide resin (A) to 330 ° C. or less, it is possible to suppress the decomposition of the polyamide resin (A) at the time of producing the polyamide resin composition, and the heat resistance, mechanical strength, and metal adhesion of the molded product. And chemical resistance can be further improved. Here, the melting point of the polyamide resin in the present invention is as follows. Using a differential scanning calorimeter, the polyamide resin is cooled from the molten state to 30 ° C. at a temperature decreasing rate of 20 ° C./min. The temperature is defined as the temperature of the endothermic peak that appears when the temperature is raised to the melting point + 40 ° C. at a rate of temperature increase of 20 ° C./min after holding for 3 minutes. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak having the highest peak intensity is defined as the melting point. Examples of the polyamide resin having a melting point of 200 ° C. to 330 ° C. include those exemplified above as the polyamide resin (A).

  Moreover, it is preferable that carbon number of the diamine residue in a polyamide resin (A) is an even number of 4-18. When using an aliphatic diamine, due to the even-odd effect, by using a diamine having an even number of carbon atoms, the crystallinity of the polyamide resin (A) is improved, and the exchange reaction under high temperature conditions is suppressed and the residence stability is improved. Can be made. As a result, the metal adhesion and chemical resistance of the molded product can be further improved. In addition, by making the diamine residue have 4 or more carbon atoms, it is possible to suppress gas generation during molding at high temperature, further improve the mold filling property, and further improve the metal adhesion of the molded product. it can. On the other hand, by setting the carbon number of the diamine residue to 18 or less, the decomposition of the polyamide resin (A) at high temperature is suppressed to improve the residence stability, and the chemical resistance under the heating condition of the molded product is further improved. Can be made. Examples of such diamines include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, and the like. Among these, 1,10-decanediamine is more preferable.

  Although there is no restriction | limiting in particular in the polymerization degree of a polyamide resin (A), It is preferable that relative viscosity is 1.5-3.5. The relative viscosity here means a value measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a polyamide resin concentration of 0.01 g / ml. When using a some polyamide resin (A) together, it is preferable that the relative viscosity as a whole polyamide resin (A) is 1.5-3.5. When the relative viscosity is 1.5 or more, the mold filling property is excellent, and the mechanical strength, metal adhesion, and chemical resistance of the obtained molded product can be further improved. 2.0 or more is more preferable. On the other hand, if the relative viscosity is 3.5 or less, the mold filling property can be further improved since the fluidity is excellent. 3.0 or less is more preferable. Examples of means for setting the relative viscosity of the polyamide resin (A) in such a range include, for example, a method of appropriately adjusting polymerization conditions such as pressure, temperature, polymerization time, etc. during production of the polyamide resin, dicarboxylic acid, diamine, end-capping agent, and the like. And a method of adjusting the raw material composition.

In the polyamide resin (A), it is preferable that 10% or more of the end groups of the molecular chain are blocked. When the terminal blocking rate is 10% or more, the mold filling property of the resin composition can be further improved. The terminal blocking rate is more preferably 20% or more. The terminal blocking rate can be determined by the following formula (1) by measuring the number of terminal carboxyl groups, terminal amino groups and terminal groups blocked by the terminal blocking agent present in the polyamide resin (A). It is preferable from the viewpoint of accuracy and simplicity that the number of each terminal unit is determined by ¹ H-NMR based on the integral value of the characteristic signal corresponding to each terminal group.
Terminal blockage rate (%) = {(XY) / X} × 100 (1)
In the above formula (1), X represents the total number of terminal groups (usually equal to twice the number of polyamide molecules), and Y represents the total number of terminal carboxyl groups and amino groups remaining unblocked. .

  The end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide. For example, monocarboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid Halides, monoesters, monoalcohols and the like can be used. A monocarboxylic acid or a monoamine is preferable from the viewpoints of reactivity and stability at the blocking end, and a monocarboxylic acid is more preferable from the viewpoint of handling. Specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid are preferable.

  As a method for producing the polyamide resin (A), for example, a raw material diamine and dicarboxylic acid or a salt thereof and, if necessary, other copolymerization components are heated to obtain a low-order condensate. Alternatively, a method of increasing the degree of polymerization by melt polymerization may be used. 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 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.

  Further, a catalyst may be added in the polymerization of the polyamide resin (A). Examples of the catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid, salts and esters thereof. The above salts or esters include metal salts with potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, ammonium salts, ethyl esters, isopropyl esters, butyl esters. Hexyl ester, stearyl ester, phenyl ester and the like.

  The polyamide resin composition of the present invention comprises a compound (B) containing a piperidinyl group, an aromatic group and an amide bond. The polyamide resin (A) improves the mechanical strength, heat resistance, and chemical resistance of the molded product, but tends to decrease fluidity due to entanglement, and tends to decrease mold filling property and metal adhesion. In the present invention, by blending the polyamide resin (A) with the compound (B), the fluidity is improved, the mold filling property is improved, the metal adhesion of the molded product is further improved, and the chemical resistance is improved. The sex can be further improved. Although it is known that the compound (B) is effective in improving the light resistance of fibers represented by polyamide 6 and polyamide 66, in the present invention, the compound (B) is blended with the polyamide resin (A). By doing so, metal adhesion and chemical resistance can be improved by polar groups such as amide bonds and piperidinyl groups. Further, the compound (B) having an amide bond and an aromatic group is excellent in compatibility with the polyamide resin (A), and further, the insertion effect of the polyamide resin (A) between molecules and within the molecule by hydrogen bonding by the piperidinyl group. Therefore, it is possible to improve the fluidity by untangling the polyamide resin (A) and suppress plasticization and decomposition, while also providing excellent mold filling during molding, and excellent metal adhesion and chemical resistance. I think it can be obtained. Furthermore, since the compound (B) is excellent in compatibility with the polyamide resin (A), the crystalline characteristics of the polyamide resin (A) can be maintained, and a molded product having excellent mechanical strength can be obtained.

  In the compound (B), the piperidinyl group may be substituted and preferably has a structure represented by the following general formula (II).

In the general formula (II), R ′ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or —COR ¹ group (R ¹ is hydrogen or an alkyl having 1 to 6 carbon atoms). Group), phenyl group, -COOR ² group (R ² is an alkyl group having 1 to 4 carbon atoms), -NR ³ R ⁴ group (R ³ and R ⁴ may be the same or different, hydrogen, 1 to carbon atoms 12 alkyl groups, cycloalkyl groups having 5 to 6 carbon atoms, phenyl groups, or alkylphenyl groups having 1 to 12 carbon atoms). Preferably it is hydrogen.

  It is preferable that a compound (B) has an amide bond couple | bonded with a piperidinyl group. That is, it preferably has a structure represented by the following general formula (III). In the general formula (III) below, R ′ is the same as R ′ in the general formula (II).

  The compound (B) preferably has an aromatic group and an amide bond that bonds to the aromatic group. As the aromatic group, an aromatic hydrocarbon group is preferable, and examples thereof include a phenylene group and a naphthylene group. Among these, a phenylene group excellent in affinity with the polyamide resin (A) is more preferable.

  As the compound (B), those having a structure represented by the following general formula (IV) are preferable.

In the general formula (IV), R ′ is the same as R ′ in the general formula (II), and R ⁵ is an optionally substituted piperidinyl group, an alkoxy group having 1 to 18 carbon atoms, halogen, aminoalkyl. Represents a group or an epoxy group having 3 to 5 carbon atoms. From the viewpoint of compatibility with the polyamide resin (A), R ⁵ preferably contains a piperidinyl group. That is, the compound (B) more preferably has a structure represented by the following general formula (I). In the following general formula (I), R ′ is the same as R ′ in general formula (II), preferably hydrogen.

  The molecular weight of the compound (B) is preferably 1000 or less, and more preferably 800 or less, from the viewpoint of compatibility with the polyamide resin (A) and the effect of inserting the polyamide resin (A) into and between the molecules.

  The production method of the compound (B) is not particularly limited. For example, as described in JP-T-2006-505524, sterically hindered amine having the structure of the general formula (II) and isophthalic acid or terephthalic acid dichloride. And the like.

  In the polyamide resin composition of the present invention, the compound (B) may react with the polyamide resin (A) and be introduced into the side chain or terminal of the polyamide resin (A), or react with the polyamide resin (A). You may keep the structure at the time of mixing | blending. Moreover, these may be mixed.

  In the polyamide resin composition of the present invention, the compounding amount of the compound (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When the compounding quantity of a compound (B) is less than 0.1 weight part, the mold filling property of a polyamide resin composition will fall, and the mechanical strength, heat resistance, metal adhesiveness, and chemical resistance of a molded article will fall. 0.5 parts by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, when the compounding amount of the compound (B) exceeds 10 parts by weight, the compound (B) bleeds out to the surface layer of the molded product, the appearance is deteriorated, or with the plasticization and decomposition foaming of the polyamide resin (A), The molding stability at the time of continuous molding of the polyamide resin composition is lowered, the mold filling property is lowered, and the mechanical strength, heat resistance, metal adhesion, and chemical resistance of the molded product are lowered. 9 parts by weight or less is preferable, 5 parts by weight or less is more preferable, and 4 parts by weight or less is more preferable.

  The polyamide resin composition of the present invention may further contain a filler (C). By blending the filler (C), the mechanical strength, heat resistance and rigidity of the molded product can be further improved, and dimensional changes such as expansion and contraction due to temperature changes can be reduced. In addition, chemical resistance can be further improved.

  The shape of the filler (C) is not particularly limited, and may be any of a fiber shape, a plate shape, a powder shape, and a granular shape. Specifically, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone coke Fibrous fillers such as fibers and metal fibers, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate and other metal silicates, silicon oxide, magnesium oxide, alumina , Metal oxides such as zirconium oxide, titanium oxide and iron oxide, metal carbonates such as calcium carbonate, magnesium carbonate and dolomite, metal sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, carbonized Silica , Metal hydroxides such as calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder, non-fibrous fillers such as carbon black, silica, graphite, montmorillonite, beidellite, nontronite, Smectite clay minerals such as saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li Examples thereof include layered silicates typified by swelling mica such as type tetrasilicon fluorine mica. Two or more of these may be blended. Moreover, the surface of the filler (C) may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agent.

  In the layered silicate, exchangeable cations existing between layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. In particular, ammonium ions are preferably used. Among the ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid, and the like are preferable.

  Layered silicates in which exchangeable cations present between layers are exchanged with organic onium ions can be produced by reacting layered silicates having exchangeable cations between layers and organic onium ions by a known method. it can. Specific examples include a method using an ion exchange reaction in a polar solvent such as water, methanol, and ethanol, and a method in which a liquid or molten ammonium salt is directly reacted with a layered silicate.

  Among these fillers, layered silicates such as glass fiber, carbon fiber, talc, wollastonite, montmorillonite, and synthetic mica are preferable, and glass fiber is particularly preferable.

  The type of glass fiber used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, and the like. Also, weakly alkaline glass fibers are excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with a coating agent or a treating agent. Examples of the coating agent or processing agent include thermoplastic resins such as ethylene / vinyl acetate copolymer, epoxy-based, urethane-based, acrylic-based coating agents or processing agents, silane-based, titanate-based coupling agents, and the like. Other surface treatment agents may be mentioned. Urethane coating agents or sizing agents, epoxy silanes, and amino silane coupling agents are particularly preferred.

  As for the compounding quantity of the filler (C) in the polyamide resin composition of this invention, 1-200 weight part is preferable with respect to 100 weight part of polyamide resin (A). By setting the blending amount of the filler (C) to 1 part by weight or more, the mechanical strength, rigidity, heat resistance, metal adhesion and chemical resistance of the molded product can be further improved. 50 parts by weight or more is preferable. On the other hand, by making the blending amount of the filler (C) 200 parts by weight or less, the mold filling property at the time of molding, the mechanical strength of the molded product, heat resistance, metal adhesion, and chemical resistance are maintained at a higher level. can do.

  In the conventional polyamide resin composition, as a filler, for example, when glass fiber is taken as an example, when the blending amount is 100 parts by weight or more with respect to 100 parts by weight of the polyamide resin, it results from a decrease in fluidity due to thickening The mechanical properties are greatly deteriorated due to the decomposition of the polyamide resin and the breakage of the glass fiber due to the remarkable heat generation during melting and kneading. On the other hand, the polyamide resin composition of the present invention suppresses the decrease in fluidity due to thickening, shearing heat generation during melt kneading, and breakage of glass fibers even when the filler contains a large amount of filler. It is possible to greatly improve the mold filling property of the polyamide resin composition, the heat resistance of the molded product, the mechanical strength, the metal adhesion, and the chemical resistance.

  A flame retardant can be further blended in the polyamide resin composition of the present invention. By blending a flame retardant, flame retardancy can be imparted, and it can be suitably used for applications that require flame retardancy, such as automobiles, electrical / electronic housings, and exterior parts. The flame retardant is not particularly limited as long as it can impart flame retardancy to the polyamide resin composition of the present invention. Specific examples include halogen-based flame retardants such as phosphorus-based flame retardants, nitrogen-based flame retardants, and metal hydroxide-based flame retardants that do not contain halogen atoms, and bromine-based flame retardants. . Two or more of these flame retardants may be blended.

  Phosphorus flame retardant is a compound containing phosphorus element, specifically, polyphosphoric acid compound such as red phosphorus, ammonium polyphosphate, melamine polyphosphate, metal phosphinate or metal diphosphinate (hereinafter referred to as these) May be described as (di) phosphinic acid metal salts), phosphazene compounds, aromatic phosphate esters, aromatic condensed phosphate esters, halogenated phosphate esters, and the like. Among these, (di) phosphinic acid metal salts are preferable. When (di) phosphinic acid metal salt is used, compared with the case where other flame retardants are used, it has the characteristic that the heat resistance fall by flame retardant addition is very small. The cause of this is not clear, but (di) phosphinic acid metal salts have higher heat resistance than other phosphorus flame retardants, and also exhibit flame retardancy with a smaller amount of addition than brominated flame retardants. Therefore, it is considered that the excellent decrease in heat resistance is suppressed. Furthermore, in the polyamide resin composition of the present invention, when (di) phosphinic acid metal salt is blended, due to the interaction between the unpaired electron of the piperidinyl group of compound (B) and the metal of (di) phosphinate. The dispersibility in the polyamide resin (A) is increased, the surface appearance is improved, and the tracking resistance is improved.

  The (di) phosphinic acid metal salt is produced in an aqueous medium using, for example, phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. The (di) phosphinate is essentially a monomeric compound, but depending on the reaction conditions, it may be a polymeric phosphinate having a degree of condensation of 1 to 3 depending on the environment. As phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and And diphenylphosphinic acid. Examples of the metal component (M) to be reacted with the phosphinic acid include metal carbonates, metal hydroxides and metal oxides containing calcium ions, magnesium ions, aluminum ions and / or zinc ions.

  Examples of phosphinic acid metal salts include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphine Zinc oxide, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, Zinc methyl-n-propylphosphinate, calcium methylphenylphosphinate, methylphenylphosphine Magnesium, aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate and the like. Examples of the diphosphinic acid metal salt include methandi (methylphosphinic acid) calcium, methanidi (methylphosphinic acid) magnesium, methandi (methylphosphinic acid) aluminum, methandi (methylphosphinic acid) zinc, benzene-1,4-di (methyl) Phosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-dimethylphosphinic acid) aluminum, benzene-1,4-di (methylphosphinic acid) zinc and the like. Two or more of these may be used.

  Among these (di) phosphinic acid salts, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable from the viewpoint of flame retardancy and electrical characteristics. In addition to these (di) phosphinates, an acid scavenger can be blended from the viewpoint of preventing mold corrosion. Examples of the acid supplement include hydrotalcite and zinc stearate.

  The phosphazene compound is an organic compound having —P═N— bond in the molecule, and examples thereof include cyclic phenoxyphosphazene, chain phenoxyphosphazene, and crosslinked phenoxyphosphazene compound. Examples of the cyclic phenoxyphosphazene compound include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffeoxycyclopentaphosphazene. Examples of the chain phenoxyphosphazene compound include compounds obtained by substituting a linear dichlorophosphazene having a polymerization degree of 3 to 10,000 obtained by reduction polymerization of the above hexachlorocyclotriphosphazene with a phenoxy group. . Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned. The content of the phenylene group in the crosslinked phenoxyphosphazene compound is preferably 70 to 90% based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene compound and / or the chain phenoxyphosphazene compound. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  Examples of the aromatic phosphate include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, and bis- (t-butylphenyl). ), Butylated phenyl phosphates such as phenyl phosphate, tris- (t-butylphenyl) phosphate, propylated phenyl phosphates such as isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate, and the like. It is done.

  Examples of the aromatic condensed phosphate ester include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and the like.

  Examples of the halogenated phosphate ester include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2chloroethyl) dichloroisopentyl diphosphate, polyoxyalkylene bis (dichloroalkyl). ) Phosphate and the like.

  Examples of nitrogen flame retardants include salts of triazine compounds with cyanuric acid or isocyanuric acid. A triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of a triazine compound and cyanuric acid or isocyanuric acid, usually 1 to 1 (molar ratio), sometimes 2 to 1 (molar ratio). ). Examples of triazine compounds include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3, 5-Triazine and the like can be mentioned, and melamine, benzoguanamine and acetoguanamine are particularly preferable. Specific examples of salts of triazine compounds with cyanuric acid or isocyanuric acid include melamine cyanurate, mono (β-cyanoethyl) isocyanurate, bis (β-cyanoethyl) isocyanurate, tris (β-cyanoethyl) isocyanurate, etc. Among them, melamine cyanurate is particularly preferable.

Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide, and magnesium hydroxide is more preferable. These are usually commercially available and are not particularly limited, such as particle diameter, specific surface area, and shape, but preferably have a particle diameter of 0.1 to 20 μm, a specific surface area of 3 to 75 m ² / g, and a shape. Is preferably spherical, needle-shaped or platelet-shaped. The metal hydroxide flame retardant may or may not be surface-treated. Examples of the surface treatment method include a treatment method in which a coating is formed with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, or an epoxy resin.

  The brominated flame retardant is not particularly limited as long as it is a compound containing bromine in the chemical structure. For example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether , Octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A and other monomeric organic bromine compounds, brominated polycarbonate (for example, brominated bisphenol A as a raw material) Produced polycarbonate oligomers or copolymers thereof with bisphenol A), brominated epoxy compounds (eg by reaction of brominated bisphenol A with epichlorohydrin). Monoepoxy compounds obtained by reaction of produced epoxy compounds and brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuric chloride and brominated phenol condensates And brominated polystyrene such as brominated polystyrene (polystyrene), poly (brominated styrene) and crosslinked brominated polystyrene, and halogenated polymeric bromine compounds such as crosslinked or non-crosslinked brominated poly (α-methylstyrene). . Of these, ethylene bis (tetrabromophthalimide), brominated epoxy polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, and brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and bromine. Polycarbonates are most preferably used.

  The blending amount of the flame retardant in the polyamide resin composition of the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When the blending amount of the flame retardant is 1 part by weight or more, the flame retardancy can be further improved. Moreover, if it is 50 weight part or less, the toughness of the molded article obtained can be improved more. When using a phosphorus-type flame retardant as a flame retardant, the compounding quantity is preferably 2-45 parts by weight, more preferably 10-40 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When using a nitrogen-type flame retardant as a flame retardant, the compounding quantity is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When a metal hydroxide flame retardant is used as the flame retardant, the amount thereof is preferably 10 to 50 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When a brominated flame retardant is used as the flame retardant, the blending amount is preferably 10 to 50 parts by weight, more preferably 15 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin (A).

  Moreover, the polyamide resin composition of the present invention may contain a flame retardant aid together with the above flame retardant, and the flame retardancy can be improved synergistically. Examples of the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony deoxydioxide, crystalline antimonic acid, sodium antimonate, lithium antimonate, barium antimonate, antimony phosphate, zinc borate, and tin. Examples include zinc oxide, basic zinc molybdate, zinc stannate, calcium zinc molybdate, molybdenum oxide, zirconium oxide, zinc oxide, iron oxide, red phosphorus, swellable graphite, and carbon black. Of these, zinc stannate, antimony trioxide, and antimony pentoxide are more preferable. The blending amount of the flame retardant aid is preferably 0.2 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin (A), from the viewpoint of flame retardancy improvement effect. .

  The polyamide resin composition of the present invention includes various types of resins, heat-resistant agents, and the like, depending on the purpose, together with the polyamide resin (A), the compound (B), and the filler (C), as long as the effects of the present invention are not impaired. Additives can be further blended.

  Specific examples of the other resins include polyester resins, polyolefin resins, modified polyphenylene ether resins, polysulfone resins, polyketone resins, polyetherimide resins, polyarylate resins, polyether sulfone resins, polyether ketone resins, polythioether ketone resins. , Polyether ether ketone resins, polyimide resins, polyamideimide resins, tetrafluoropolyethylene resins, polyamide resins other than the polyamide resin (A), and the like. Examples of the polyamide resin other than the polyamide resin (A) include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), and polytetramethylene adipa. Amide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polytetramethylene sebacamide (polyamide 410), polyhexamethylene dodecamide (polyamide 612), poly Mention may be made of aliphatic polyamide resins such as undecanamide (polyamide 11), polydodecanamide (polyamide 12), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66). When blending these resins, the blending amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the polyamide resin (A).

  Examples of the heat-resistant agent include phenolic compounds, phosphorus compounds, and copper compounds. In addition, it is particularly preferable to use a phenolic compound and a phosphorus compound in combination because the heat resistance, thermal stability, and fluidity retention effect are particularly large.

  As the phenolic compound, a hindered phenolic compound is preferably used. For example, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and the like are preferably used. The blending amount of the phenolic compound is preferably 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin (A) from the viewpoint of heat resistance improvement effect, and 1 part by weight from the viewpoint of gas components generated during molding. The following is preferred.

  Examples of phosphorus compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol-di. -Phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) ) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester and the like. Among them, those having a high melting point are preferably used in order to reduce volatilization and decomposition of the heat-resistant agent during the production of the polyamide resin composition. The amount of the phosphorus compound is preferably 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin (A) from the viewpoint of heat resistance improvement effect, and 1 part by weight from the viewpoint of gas components generated during molding. The following is preferred.

  Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid. Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate, inorganic copper halide and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. 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 preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin (A). If the blending amount is 2 parts by weight or less, the release and coloring of metallic copper during melt molding can be suppressed. In this invention, it is also possible to mix | blend an alkali halide with a copper compound. As the alkali halide compound, potassium iodide and sodium iodide are preferable.

  Other additives include UV absorbers (resorcinol, salicylate, etc.), anti-coloring agents such as phosphites, hypophosphites, lubricants and mold release agents (stearic acid, montanic acid and metal salts thereof, esters thereof, The usual additives such as carbon black, crystal nucleating agent, plasticizer, lubricant and antistatic agent as colorants including dyes and pigments, conductive agents or colorants, such as half esters, stearyl alcohol, stearamide and polyethylene wax) Can be mentioned.

  Next, the manufacturing method of the polyamide resin composition of this invention is demonstrated. The polyamide resin composition of the present invention can be obtained by, for example, a method of kneading each component in a molten state or a method of mixing in a solution state. The compound (B) may be added to the polyamide resin in a pressure vessel such as a polymerization can at the time of solution polymerization, solid phase polymerization or melt polymerization, and the obtained polyamide resin and the compound (B) may be added to other components as necessary. At the same time, it may be kneaded in a molten state or mixed in a solution state. From the viewpoint of handling properties, a method of kneading the polyamide resin (A), the compound (B) and other components as necessary in a molten state is preferable. Examples of the kneading method in the molten state include melt kneading using an extruder and melt kneading using a kneader. From the viewpoint of productivity, melt kneading using an extruder that can be continuously manufactured is preferable. Examples of the extruder include those exemplified as the extruder used for increasing the degree of melt polymerization in the polyamide resin production method, and a twin-screw extruder is preferable.

  As a melt-kneading method using an extruder, a polyamide resin (A), a compound (B), a method of kneading a filler (C) and other additives as necessary (collective kneading method), a polyamide resin (A), Method of melt-kneading compound (B) and other additives as required, and then further adding filler (C) and other additives as required using a side feeder or the like (side feeder) Law). When blending the filler (C), the polyamide resin (A), the compound (B), and other additives as necessary are melt-kneaded in advance, and these are fully interacted to increase the compatibility. The side feeder method is preferable in that the filler (C) can be supplied.

  When producing a polyamide resin composition by melt-kneading using a twin screw extruder, the ratio (L / D) of the total screw length L and screw diameter D of the twin screw extruder is preferably 25 or more, More than 30 is more preferable. When the L / D is 25 or more, after the polyamide resin (A) and the compound (B) are sufficiently kneaded, it becomes easy to supply the filler (C) and other additives as necessary. As a result, the polyamide resin (A) and the compound (B) are mixed more uniformly, and the mold filling property at the time of molding the polyamide resin composition, the heat resistance of the molded product, the mechanical strength, the metal adhesion, and the chemical resistance are improved. It can be improved further.

  The polyamide resin composition and molded product thereof of the present invention are utilized for various applications such as automobile parts, electrical / electronic parts, building materials, sports equipment, various containers, daily necessities, daily life goods and hygiene goods, taking advantage of their excellent characteristics. be able to.

  Automobile parts include, for example, engine covers, air intake pipes, timing belt covers, intake manifolds, filler caps, throttle bodies, cooling fans and other automotive engine peripheral parts, cooling fans, radiator tank tops and bases, cylinder head covers, oil Automotive underhood parts such as pans, brake piping, fuel piping tubes, waste gas system parts, automobile gear parts such as gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners, shift lever brackets, steering lock brackets, Key cylinder, door inner handle, door handle cowl, interior mirror bracket, air conditioner switch, instrument panel Automotive interior parts such as console box, glove box, steering wheel, trim, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror stay, tailgate panel, license garnish, roof rail, engine mount bracket, rear garnish, rear spoiler , Trunk lid, rocker molding, molding, lamp housing, front grille, mudguard, side bumper and other automotive exterior parts, air intake manifold, intercooler inlet, exhaust pipe cover, inner bush, bearing retainer, engine mount, engine head cover, resonator, And intake and exhaust system parts such as throttle bodies, chains Engine cooling water system parts such as bars, thermostat housings, outlet pipes, radiator tanks, oil netters, and delivery pipes, connectors and wire harness connectors, motor parts, lamp sockets, sensor on-board switches, combination switches, etc. be able to.

  Examples of electrical / electronic components include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other pole rods, electrical components , Motor cases, notebook computer 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. Electrical components: 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, printed boards, Tuner Electronic parts such as 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. .

  Building materials include, for example, civil engineering building walls, roofs, ceiling material-related parts, window material-related parts, heat insulation-related parts, flooring-related parts, seismic isolation / vibration-related parts, lifeline-related parts, etc. Can be mentioned.

  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 line related products such as fishing lines, summer sports related products such as surfing, winter sports related products such as skiing and snowboarding, and other indoor and outdoor sports related products.

  Especially, it is preferably used for automobile engine peripheral parts, automobile under hood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake / exhaust system parts, engine cooling water system parts and electrical / electronic parts, and automobile interior parts and automobile exterior parts. It is particularly preferably used for electrical and electronic component applications.

The present invention will be described more specifically with reference to the following examples. The characteristic evaluation was performed according to the following method. In addition, this invention is not limited to the following Example.

  The polyamide resin (A) used in the examples and comparative examples is as follows.

Production Example 1: (A-1) Polyamide 10T
Decamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are added in an equimolar amount so that the total amount becomes 10 kg, and further 0.5 mol% with respect to the total amount of decamethylenediamine. Was added in excess, and 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials. The mixture was charged in a pressure vessel, sealed, and purged with nitrogen. Heating was started while the pressure vessel was sealed, and the temperature was raised to 240 ° C. over 2.5 hours. After the can internal pressure reached 2.0 MPa, the internal pressure of the can 2 was released while releasing moisture out of the system. The pressure was maintained at 0.0 MPa and a can internal temperature of 240 ° C. for 2.5 hours. Thereafter, the contents were discharged from the pressurized container to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid-phase polymerized at 50 Pa and 240 ° C. to obtain a polyamide 10T having a relative viscosity of 2.48 and a melting point of 315 ° C. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit of the polymer calculated from the charging ratio was 25.1%.

Production Example 2: (A-2) Polyamide 10T / 612
A diamine mixture was prepared by mixing decamethylenediamine (Tokyo Chemical Industry Co., Ltd.), which is a diamine component, and hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) so that the molar ratio was 91: 9. Also, terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which are dicarboxylic acid components, were mixed at a molar ratio of 91: 9 to prepare a dicarboxylic acid mixed solution. Prepared. The diamine mixed solution and the dicarboxylic acid mixed solution were added so that the total amount of the diamine component and the dicarboxylic acid component was equal to 10 kg and an equimolar amount. Further, 0.5 mol% of a mixture of decamethylene diamine and hexamethylene diamine (91/9 (mol% ratio)) was excessively added to the total amount of decamethylene diamine, and the total amount of these raw materials was 70 parts by weight. Then, 30 parts by weight of water was added and mixed, charged in a pressure vessel, sealed, and purged with nitrogen. Heating was started while the pressure vessel was sealed, the temperature was raised to 240 ° C. over 2.0 hours, and after the internal pressure of the can reached 2.0 MPa, the internal pressure of the can was released while releasing moisture out of the system. It was kept at 2.0 MPa and a can internal temperature of 240 ° C. for 2 hours. Thereafter, the contents were discharged from the pressurized container to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid phase polymerized at 50 Pa and 240 ° C. to obtain polyamide 10T / 612 having a relative viscosity of 2.43 and a melting point of 289 ° C. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit of the polymer calculated from the charging ratio was 22.8%.

(A-3) Polyamide 66 / 6I / 6
A polyamide having a melting point of 228 ° C., a relative viscosity of 2.70, and a copolymerization ratio of 66 / 6I / 6 = 76/17/7% by weight was used. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit of the polymer calculated from the copolymerization ratio was 5.8%.

(A-4) Polyamide MXD6
Polyamide MXD6 resin “Reny” (registered trademark) # 6002 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) having a melting point of 238 ° C. was used. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit was 30.9%.

(A′-5) Polyamide 66
A polyamide 66 resin having a melting point of 265 ° C. and a relative viscosity of 2.70 was used. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit was 0%.

Production Example 3: (A′-6) Polyamide 46
Nylon 46 salt 700 g, tetramethylenediamine 5.27 g, sodium hypophosphite monohydrate 0.2962 g, and ion-exchanged water 70 g were charged into a 3 L pressure vessel with a stirring blade and sealed, and the atmosphere was replaced with nitrogen. did. Heating was started while the pressure vessel was sealed, and after reaching an internal temperature of 225 ° C. and 1.5 MPa, the internal pressure of the can was maintained at 1.5 MPa for 30 minutes while water was released outside the system. Thereafter, the contents were discharged from the pressurized container onto a cooling belt to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized, vacuum dried at 80 ° C. for 24 hours, and solid-phase polymerized at 250 ° C. and 100 Pa for 15 hours to obtain polyamide 46 having a relative viscosity of 2.80 and a melting point of 290 ° C. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit of the polymer calculated from the charging ratio was 0%.

(A'-7) Polyamide 6/66/610
A polyamide having a melting point of 158 ° C., a relative viscosity of 2.65, and a copolymerization ratio of 6/66/610 = 40/35/25% by weight was used. The ratio of the total molecular weight of the aromatic group and alicyclic group to the molecular weight per structural unit of the polymer calculated from the copolymerization ratio was 0%.

Production Example 4: (B-1) N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) 1,4-benzenedicarboxamide Stirrer, dropping funnel, thermometer and pH electrode In a 2 liter four-necked flask with 158.1 g (1.02 mol) 2,2,6,6-tetramethylpiperidin-4-yl-amine and 93.8 g crushed ice at a temperature of 7 ° C. Cooled to. While stirring, 102.1 g (0.50 mol) of molten terephthalic acid chloride was added by a dropping funnel. During the addition of terephthalic acid chloride, the temperature of the reaction mixture was kept below 10 ° C. After adding terephthalic acid chloride, the reaction mixture was diluted with 450.0 g of ion exchange water and 133.3 g of 30% NaOH solution (1.0 mol). While adding NaOH, an additional 300.0 g of ion exchange water was added to dilute the reaction mixture. After stirring for 3 hours at 25 ° C., the suspension was suction filtered on a filter and washed until pH 10 was reached. The cake on the filter was dispersed again in 600.0 g of ion exchange water, stirred for 30 minutes, isolated by suction filtration on the filter again, and washed with 700.0 g of ion exchange water. The obtained reaction product was dried overnight at 50 ° C. in a vacuum dryer. The molecular weight of the obtained compound was 443.

(B′-2) Bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate
Tinuvin 770 (manufactured by BASF) was used. The molecular weight of the compound was 481.

Production Example 5: (B′-3) Bisphenol A ethylene oxide-added helicosyl acid diester Ethylene with respect to 1 mol of bisphenol A in a 2 liter four-necked flask equipped with a nitrogen introduction tube, a distillation tube, a stirrer and a thermometer Reaction product added with 2 mol of oxide (2,2-bis [4- (2-hydroxyethoxy) phenyl] propane: NEWCOL1900 manufactured by Nippon Emulsifier Co., Ltd.) with respect to 474.4 g (1.5 mol), heicosilic acid (C ₂₁ H ₄₂ O ₂ ) (326 g, 3 mol) was added, and the mixture was stirred at 210 ° C. for 8 hours using tin powder as a catalyst. Thereafter, the esterification reaction was completed by dehydration under reduced pressure, and the resulting product was cooled to room temperature to obtain bisphenol A ethylene oxide-added helicosyl acid diester. The molecular weight of the obtained compound was 932.

Production Example 6: (B′-4) Amide oligomer composed of stearic acid, ethylenediamine and adipic acid In a four-necked flask equipped with a nitrogen introduction tube, a distilling tube and a dropping funnel, 660.0 g of stearic acid (in a nitrogen atmosphere) 2.32 mol) and 169.4 g (1.16 mol) of adipic acid were charged, and the mixture was heated to 190 ° C. and completely dissolved. Thereafter, 139.2 g (2.32 mol) of ethylenediamine was added through a dropping funnel over 30 minutes. After completion of the addition of ethylenediamine, the temperature of the reaction mixture is raised to 230 ° C., the reaction is terminated when a predetermined amount of water produced by the reaction is distilled off, and the resulting product is cooled to room temperature, An oligomer was obtained. The molecular weight of the obtained compound was 790.

  (C-1) Surface-treated glass fiber “T-275H” (manufactured by Nippon Electric Glass, T-275H, cross-sectional diameter of 10.5 μm, fiber length of 3 mm) was used.

  (D-1) A phosphorus-based flame retardant (aluminum diethylphosphinate “OP1230” manufactured by Clariant) was used.

  (E-1) Hydrotalcite (kw-2100 manufactured by Kyowa Chemical Co., Ltd.) was used.

  Characteristic evaluation in each example and comparative example was performed according to the following method.

[Relative viscosity of polyamide resin]
The relative viscosity (ηr) was measured using an Ostwald viscometer at 25 ° C. in 98% concentrated sulfuric acid having a polyamide resin concentration of 0.01 g / ml.

[Melting point of polyamide resin]
About 5 mg of polyamide resin was sampled, and the melting point of the polyamide resin was measured under the following conditions using a Seiko Instruments robot DSC (differential scanning calorimeter) RDC220 under a nitrogen atmosphere. After the temperature was raised to the melting point of the polyamide resin + 40 ° C. to obtain a molten state, the temperature was lowered to 30 ° C. at a rate of temperature reduction of 20 ° C./min, followed by holding at 30 ° C. for 3 minutes and then 20 ° C./min. The temperature (melting point) of the endothermic peak observed when the temperature was raised to the melting point + 40 ° C. at the rate of temperature rise was determined.

[Mold filling property]
When (A-1) polyamide 10T or (A-2) polyamide 10T / 612 was used, the pellets obtained in each example and comparative example were 140 ° C., (A-3) polyamide 66 / 6I / 6, When (A′-5) polyamide 66 or (A′-7) polyamide 6/66/610 is used, 80 ° C., (A-4) polyamide MXD6, (A′-6) when polyamide 46 is used Vacuum drying at 110 ° C. for 12 hours, using a ROBOSHOTα-30C (manufactured by FANUC) injection molding machine, setting the cylinder set temperature to the melting point of the polyamide resin + 15 ° C., and setting the mold temperature to (A-1) polyamide 10T Or (A-2) 140 ° C. when polyamide 10T / 612 is used, (A-3) polyamide 66/6 I / 6, (A′-5) polyamide 66: 80 ° C. or (A′-7) 80 ° C when using Liamide 6/66/610, 110 ° C when using (A-4) Polyamide MXD6, (A'-6) Polyamide 46, injection speed 100mm / sec, injection pressure Was formed by injection molding using a 200 mm long × 10 mm wide × 0.5 mm thick mold under the condition of 98 MPa to produce a 10 mm wide × 0.5 mm thick rod flow test piece. However, when two or more polyamide resins were used, the vacuum drying temperature and the mold setting temperature were set to the higher temperature, and the cylinder setting temperature was set to the melting point of the resin having a high melting point + 15 ° C. For each of the five samples, the rod flow length at a holding pressure of 0 was measured, the average value was obtained, and the fluidity was evaluated. The longer the flow length, the better the fluidity.

  In addition, SG75H-MIV (Sumitomo Heavy Industries, Ltd.) injection in which the pellets obtained in each Example and Comparative Example were vacuum-dried under the same conditions as above and set to the same cylinder temperature and mold temperature as above. Using a molding machine, 20 cycles of 1/8 inch thick ASTM No. 1 dumbbell specimens were molded in a molding cycle of screw rotation speed: 150 rpm, injection / cooling time / intermediate: 10/10/4 sec. The cushion amount was measured and the standard deviation of the cushion amount was determined. The cushion amount refers to the distance from the nozzle to the screw when the molded product is molded by the injection molding machine, and is an index representing the amount of resin remaining in the cylinder between the screw tip and the molding machine nozzle after molding. In order to suppress defects such as sink marks of molded products, it is common to supply an excess resin composition relative to the mold volume and leave a surplus of the resin composition at the tip of the cylinder. Is an index representing the amount of the surplus resin composition. In this evaluation, the resin composition including the surplus corresponding to the cushion amount of 5 mm was measured, and the molding stability was evaluated from the variation of the actual cushion amount. The longer the flow length and the smaller the standard deviation of the cushion amount during continuous molding, the better the mold filling property.

[Mechanical strength]
SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) injection molding, in which the pellets obtained in each Example and Comparative Example were vacuum-dried under the same conditions as above and set to the same cylinder temperature and mold temperature as above. Injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 1/8 inch thick ASTM No. 1 dumbbell test piece was injected under the conditions of minimum pressure + 10 MPa to fill the cavity Molded. For each of these three test pieces, a tensile test was performed at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec) according to ASTM D638, and the tensile strength was measured. Asked.

[Heat-resistant]
SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) injection molding, in which the pellets obtained in each Example and Comparative Example were vacuum-dried under the same conditions as above and set to the same cylinder temperature and mold temperature as above. Injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 1/8 inch thick ASTM No. 1 dumbbell test piece was injected under the conditions of minimum pressure + 10 MPa to fill the cavity Molded. In accordance with ASTM648, the thermal deformation temperature (load deflection temperature) was measured edgewise under test conditions of a test load of 1.82 MPa.

[Metal adhesion]
The pellets obtained in each Example and Comparative Example were vacuum-dried under the same conditions as described above, and using a hot press machine, a sheet having a thickness of 200 μm was produced under the condition of melting point + 20 ° C., and a 30 mm × 50 mm sample was cut out. It was. Thereafter, the sample is sandwiched between two aluminum plates of 30 mm × 100 mm × 1 mm thickness, and the melting point of the polyamide resin used is + 20 ° C. with a hot press machine (however, when two or more polyamide resins are used, the melting point) The sample was preheated for 5 seconds under the condition of a high melting point resin + 20 ° C. and then heated for 3 minutes under a pressure of 10 MPa to bond the sample and the aluminum plate to produce an evaluation test piece. For each of these three test pieces, one of the bonded aluminum plates was bent into a T-shape, a tensile tester was used to conduct a tensile test at a chuck distance of 10 mm and a crosshead speed of 10 mm / min, and the tensile strength was measured. The average value was obtained.

[chemical resistance]
SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) injection molding, in which the pellets obtained in each Example and Comparative Example were vacuum-dried under the same conditions as above and set to the same cylinder temperature and mold temperature as above. Injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 1/8 inch thick ASTM No. 1 dumbbell test piece was injected under the conditions of minimum pressure + 10 MPa to fill the cavity Molded. This test piece was heat-treated at 130 ° C. for 2000 hours in a 50% by volume aqueous solution of genuine super long life coolant (LLC) manufactured by Toyota Corporation having an ethylene glycol content of 88% by weight. After that, according to ASTM D638, a tensile test was performed at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec Co., Ltd.), and the tensile strength was measured. The value was determined. The ratio of the tensile strength after treatment to the tensile strength before treatment measured in the above [mechanical strength] was calculated as the tensile strength retention rate, and the chemical resistance was evaluated.

[Tracking resistance]
SG75H-MIV (manufactured by Sumitomo Heavy Industries, Ltd.) injection molding, in which the pellets obtained in each example and comparative example were vacuum-dried under the same conditions as above and set to the same cylinder temperature and mold temperature as above. Injecting / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: square plate (film gate) of 80 mm x 80 mm x 3 mm thickness under conditions of minimum pressure + 10 MPa for filling the cavity Injection molded. About the obtained square plate, according to IEC60112, the comparative tracking index | exponent CTI value was evaluated using the tracking-proof evaluation apparatus (made by Tokyo Seiden Co., Ltd.). The chemical was a 0.1% NH 4 Cl aqueous solution, and the conditions were 4.2 mm between electrode terminals, electrolyte amount 20 ± 3 mm ³ , electrolyte interval 30 seconds, 60 drops, current 1A.

(Examples 1-10, Comparative Examples 1-8)
After premixing the components shown in Tables 1-2 at the ratios shown in Tables 1-2, the cylinder temperature is the melting point of the polyamide resin + 15 ° C. (However, when two or more polyamide resins are used, Melting point + 15 ° C.), and the screw rotation speed was set to 200 rpm, and supplied to the twin screw extruder from the main feeder of TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel Works, and melt kneaded. This main feeder is connected to a position 0 when viewed from the upstream side when the total length of the screw is 1.0, that is, a position of an end portion on the upstream side of the screw segment. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The result of having evaluated various characteristics by the said method is shown to Tables 1-2.

(Examples 11 to 18, Comparative Example 9)
After premixing the components shown in Table 3 in the proportions shown in Table 3, the cylinder temperature is the melting point of the polyamide resin + 15 ° C (however, when two or more polyamide resins are used, the melting point of the resin having a high melting point + 15 ° C) The screw was supplied from the main feeder of a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd. with a screw rotation speed set to 200 rpm, and melt kneaded. Subsequently, (A) The filler (C) was supplied from the side feeder to the twin-screw extruder at a ratio shown in Table 2 with respect to 100 parts by weight of the polyamide resin, and melt kneading was performed. The side feeder is located at a position of 0.65 when viewed from the upstream side when the total length of the screw is 1.0, that is, downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. Table 3 shows the results of various characteristics evaluated by the above method.

(Examples 19 to 20, Comparative Example 10)
After preliminarily mixing the polyamide resin (A), the compound (B) or (B ′), the flame retardant (D), and the additive (E) at the ratio shown in Table 4, the cylinder temperature is adjusted to the melting point of the polyamide resin (A) +15 It was supplied from a main feeder of a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel Works, which was set at 200 ° C. and a screw rotation speed, and melt kneaded. The side feeder is located at a position of 0.65 when viewed from the upstream side when the total length of the screw is 1.0, that is, downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. Table 4 shows the results of various characteristics evaluated by the above method.

  From the comparison between Examples 1 to 4 and Comparative Examples 1 and 2, the polyamide resin (A) was blended with a specific amount of the specific compound (B) defined in the present invention, thereby filling the mold during molding. It can be seen that a molded product excellent in heat resistance, mechanical strength, metal adhesion, and chemical resistance of the molded product can be obtained.

  From the comparison between Examples 2, 5 to 10 and Comparative Examples 3 to 5, the mold filling at the time of molding is not performed until the polyamide resin (A) is blended with the specific compound (B) defined in the present invention. It can be seen that a molded product excellent in heat resistance, heat resistance, mechanical strength, metal adhesion, and chemical resistance can be obtained. Moreover, from the comparison between Examples 2, 5 to 10 and Comparative Examples 6 to 8, the effect of the present invention is exhibited only when the compound (B) is blended with the specific polyamide resin (A) defined in the present invention. I understand that.

  When the present invention was applied to a glass fiber reinforced system, the comparison between Examples 11 to 15 and Comparative Example 9 shows that the glass fiber reinforced system is excellent in mold filling property, and heat resistance, mechanical strength, and metal of the obtained molded product. It can be seen that adhesion and chemical resistance are improved. In the conventional polyamide resin composition, when the compounding amount of the glass fiber is 100 parts by weight or more with respect to 100 parts by weight of the polyamide resin, the polyamide resin is caused by remarkable shearing heat generation at the time of melt kneading due to decrease in fluidity due to thickening. Degradation of the glass fiber and breakage of the glass fiber cause a decrease in mold filling property and mechanical strength. On the other hand, the polyamide resin composition of the present invention suppresses degradation of fluidity due to thickening, decomposition due to shear heat generation during melt kneading, and breakage of glass fibers even when it contains a large amount of glass fibers. In addition, the mold filling property of the polyamide resin composition is excellent, and the heat resistance, mechanical strength, metal adhesion, and chemical resistance of the molded product can be greatly improved.

  When the present invention was applied to a flame retardant system, from the results of Examples 19 and 20 and Comparative Example 10, by adding the compound (B) to the flame retardant polyamide resin composition, It turns out that the fall of tracking property can be suppressed.

Claims (5)

100 parts by weight of a polyamide resin (A) having a structural unit containing at least a diamine residue and a dicarboxylic acid residue, and containing an aliphatic group, an aromatic group and / or an alicyclic group in the structural unit On the other hand, a polyamide resin composition comprising 0.1 to 10 parts by weight of a compound (B) containing a piperidinyl group, an aromatic group and an amide bond. The polyamide resin composition according to claim 1, wherein the compound (B) has a structure represented by the following general formula (1).

In the general formula (I), R ′ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or —COR ¹ group (R ¹ is hydrogen or an alkyl having 1 to 6 carbon atoms). Group), phenyl group, -COOR ² group (R ² is an alkyl group having 1 to 4 carbon atoms), -NR ³ R ⁴ group (R ³ and R ⁴ may be the same or different, hydrogen, 1 to carbon atoms 12 alkyl groups, cycloalkyl groups having 5 to 6 carbon atoms, phenyl groups, or alkylphenyl groups having 1 to 12 carbon atoms). However, the plurality of R ′ may be the same or different. The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin (A) has an even number of 4 to 18 carbon atoms in the diamine residue. The polyamide resin composition according to any one of claims 1 to 3, wherein (C) 1 to 200 parts by weight of a filler is further blended with 100 parts by weight of the polyamide resin (A). A molded product obtained by injection molding the polyamide resin composition according to claim 1.