TW202144496A - Flame-retardant polyamide resin composition - Google Patents

Abstract

The present invention aims to provide a flame retardant polyamide resin composition which exhibits reduced mold corrosion while keeping high heat resistance and high flame retardancy suitable for reflow-soldering process, and which is excellent in mechanical properties, bleedout resistance, low-water absorbency, and fluidity, and which is suitable for electric/electronic parts as well as housing parts. According to the present invention, there is provided a flame-retardant polyamide resin composition comprising 20-70 mass % of a semi-aromatic polyamide resin (A), 5-15 mass % of a halogen group-containing flame-retardant (B), 0.5-15 mass % of at least one metal salt-based auxiliary (C) for the flame-retardant selected from the group of consisting of zinc stannate, zinc borate, zinc phosphate, calcium borate, and calcium molybdate, 20-60 mass % of an inorganic reinforcement (D), and 0.5-5 mass % of a metal oxide (E) consisting of an oxide of bismuth.

Description

Flame retardant polyamide resin composition

The present invention relates to a flame retardant that is excellent in mechanical properties such as toughness, tensile strength, and tensile elongation, heat resistance, flame retardancy, low water absorption, exudation resistance, and fluidity, although a halogen group-containing flame retardant is used. It is a flame-retardant polyamide resin composition that reduces mold corrosion due to less corrosive gas generation during molding.

Polyamide resins are widely used in clothing, fibers for industrial materials, engineering plastics, etc. by taking advantage of their excellent mechanical properties and ease of melt molding. In particular, as engineering plastics, it is not limited to automotive components and industrial machinery components, but is widely used in various industrial components, housing components, electrical and electronic components, and the like.

Regarding electrical and electronic components, in recent years, surface mounting methods (flow method, reflow method) have rapidly penetrated due to the miniaturization of components, the high density of mounting, the simplification of steps, and the reduction of cost in recent years. In the surface mounting method, from the point of view that the process ambient temperature is higher than the solder melting temperature (240-260°C), the resin used must also pursue heat resistance at the above ambient temperature. In addition, in the surface mounting step, the swelling and deformation of the mounting element due to the water absorption of the resin may become a problem, and low water absorption is required for the resin to be used. As resins satisfying these properties, aromatic polyamides including 6T-based polyamides are used for surface-mounted electrical and electronic components.

On the other hand, depending on the location and environment in which the molded product is used, the polyamide resin used as the raw material is expected to have flame retardancy based on the UL-94 standard. In response to such a need, various proposals for imparting flame retardancy to polyamide resins have been made so far.

For example, Patent Document 1 describes that a halogenated organic compound such as brominated polystyrene, which is a flame retardant, and antimony trioxide, which functions as a flame retardant aid, are used together as a technique for flame retardant polyamide resin. This technology can impart excellent flame retardancy, but the use of antimony as a plastic product is gradually limited because of the use of antimony, which is a heavy metal that has concerns about its effects on the human body. In addition, antimony trioxide has a problem of lack of stability at the processing temperature of high-melting polyamide. Therefore, the use of flame-retardant resins using metal salts instead of antimony trioxide has been actively studied. In fact, Patent Document 2 describes an example in which zinc stannate or the like is used in place of antimony trioxide in semi-aromatic polyamide.

Compounds such as zinc and tin are gradually being used as metal substitutes for antimony, which is a flame retardant aid. However, in order to impart sufficient flame retardancy to polyamide resins, a large amount of halogen-containing flame retardants must be added. However, the flame retardant resin composition based on the semi-aromatic polyamide resin with a high melting point of 280°C or higher has a very high molding temperature, so the halogen group contained in the halogen group-containing flame retardant will not be formed during molding. The halogen gas is generated due to partial separation during processing, and the mold is corroded by the halogen gas.

In order to solve the above problems, Patent Document 3 proposes a combination of a specific brominated polystyrene polymerized from a dibrominated styrene monomer and a halogenated flame retardant containing polyamide 4 and 6 resin compositions. Hydrotalcite type, but does not achieve sufficient mold corrosion reduction.

As described above, the halogen-based flame-retardant polyamide resin composition proposed in the past cannot have both high heat resistance and high flame retardancy and reduced mold corrosion, and it is currently in use despite being problematic. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 1-115956 [Patent Document 2] WO2015/056765 [Patent Document 3] Japanese Patent Laid-Open No. 6-345963

[The problem to be solved by the invention]

The present invention was conceived in view of the above-mentioned problems of the prior art, and its object is to provide a reflow process suitable for reflow process with high heat resistance and high flame retardancy and reduced mold corrosion, furthermore, mechanical properties, exudation resistance, low water absorption A flame-retardant polyamide resin composition suitable for electrical and electronic components and housing components with excellent properties and fluidity. [Means to solve the problem]

The inventors of the present invention have made intensive studies to achieve the above-mentioned object, and as a result, they have found that in a polyamide resin composition comprising a high melting point semi-aromatic polyamide resin, a halogen group-containing flame retardant, and a conventional flame retardant auxiliary , By using specific metal oxides in addition to the conventional flame retardant additives, high flame retardancy can be achieved even if the amount of halogen-containing flame retardants used is small, so the halogen-containing flame retardants can be reduced. As a result, all desired physical properties can be achieved at a high level without the occurrence of mold corrosion caused by halogen gas, thereby completing the present invention.

The present invention has been completed based on the above-mentioned knowledge, and is constituted by the following (1) to (8). (1) A flame-retardant polyamide resin composition characterized by containing 20 to 70% by mass, 5 to 15% by mass, 0.5 to 15% by mass, 20 to 60% by mass, and 0.5 to 5% by mass, respectively The ratio contains semi-aromatic polyamide resin (A), halogen-containing flame retardant (B), at least one selected from the group consisting of zinc stannate, zinc borate, zinc phosphate, calcium borate, and calcium molybdate A metal salt-based flame retardant auxiliary (C), an inorganic reinforcing material (D), and a metal oxide (E) composed of an oxide of bismuth. (2) The flame-retardant polyamide resin composition according to (1), wherein the semi-aromatic polyamide resin (A) contains 50 mol% or more of a diamine having 2 to 12 carbon atoms and a paraben The structural unit obtained from the equivalent molar salt of phthalic acid is obtained by copolymerizing one or more of aminocarboxylic acids with 11 to 18 carbon atoms or lactamides with 11 to 18 carbon atoms. (3) The flame-retardant polyamide resin composition according to (1) or (2), wherein the semi-aromatic polyamide resin (A) is obtained by mixing (a) 50 to 99 mol% of hexamethylenediol A structural unit obtained from an equivalent molar salt of an amine and terephthalic acid, and (b) 1 to 50 mol % of a structural unit obtained from 11-aminoundecanoic acid or undecylamide are used as structural components. (4) The flame-retardant polyamide resin composition according to any one of (1) to (3), wherein the halogen-containing flame retardant (B) is a brominated polystyrene. (5) The flame-retardant polyamide resin composition according to any one of (1) to (4), wherein the bromine content of the brominated polystyrene is 62 to 72 mass %, and the weight average molecular weight is 4000 to 4000 8000, and the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) is 1.05 to 1.40. (6) The flame-retardant polyamide resin composition according to any one of (1) to (5), wherein the inorganic reinforcing material (D) is glass fiber. (7) An electrical and electronic device characterized by being formed using the flame-retardant polyamide resin composition according to any one of (1) to (6). (8) A case member characterized by being formed using the flame-retardant polyamide resin composition according to any one of (1) to (6). [Effect of invention]

The flame-retardant polyamide resin composition of the present invention has high heat resistance, and by using a specific metal oxide in addition to the conventional flame-retardant auxiliary agent, it can maintain excellent flame retardancy and reduce flame retardancy containing halogen groups. dosage of the agent. Therefore, the amount of halogen gas generated from the halogen-based flame retardant during molding can be reduced, and mold corrosion can be reduced. Furthermore, it has excellent fluidity during molding, can suppress the generation of exudates on the surface of molded articles under actual use environments such as high temperature and humidity, and can also reduce strength reduction and dimensional changes due to water absorption by polyamide resins. Therefore, according to the present invention, it is possible to provide a product highly satisfying the needs of the user.

The polyamide resin composition of the present invention is suitable for use in electrical and electronic equipment, electrical and electronic components mounted on automobiles, and housings of electrical equipment. The polyamide resin composition of the present invention can be used, for example, to form the following by injection molding: connectors, switches, IC and LED housings, sockets, relays, resistors, capacitors, coil formers, various housing components Wait.

The polyamide resin composition of the present invention contains semi-aromatic polyamides in proportions of 20 to 70 mass %, 5 to 15 mass %, 0.5 to 15 mass %, 20 to 60 mass %, and 0.5 to 5 mass %, respectively. Amine resin (A), halogen group-containing flame retardant (B), at least one metal salt-based flame retardant selected from the group consisting of zinc stannate, zinc borate, zinc phosphate, calcium borate, and calcium molybdate A combustion aid (C), an inorganic reinforcing material (D), and at least one metal oxide (E) selected from the group consisting of oxides of bismuth, aluminum, titanium, and iron.

The polyamide resin composition of the present invention is preferably a surface mount technology that corresponds to a common manufacturing method used in electrical and electronic components. Therefore, it is preferable that the melting point measured by the method described in the item of the examples described later is 290 to 350°C. Here, the melting point of the polyamide resin composition is derived from the melting peak temperature at the lowest temperature side among the melting peak temperatures measured by DSC (differential scanning calorimeter) of the polyamide resin of the polyamide resin composition. . The melting point is more preferably 300°C to 340°C, and more preferably 310°C to 340°C. When the melting point exceeds the above upper limit, the processing temperature necessary for injection molding of the polyamide resin composition of the present invention becomes extremely high, so that the polyamide resin composition is thermally decomposed, and the objective cannot be obtained. Possibilities of performance and appearance. In addition, when the melting point is less than the above-mentioned lower limit, heat resistance in the surface mounting step (230 to 280° C.) is insufficient, and defects such as product deformation during the step may occur.

The polyamide resin composition of the present invention pursues: along with the miniaturization and densification of electrical and electronic components, the strength and size of the product can be stably maintained after the product absorbs water under the actual use environment. Therefore, it is preferable that the equilibrium water absorption rate in water measured by the method described in the item of Examples described later satisfies 3.0% or less. The equilibrium water absorption rate in water is more preferably 2.5% or less, and further more preferably 2.0% or less. When the equilibrium water absorption rate in water is greater than the above-mentioned upper limit, the strength decreases due to water absorption, the dimensional change becomes significant, and bubbles are generated during the reflow process, resulting in insufficient strength of the product, poor assembly and other problems.

The semi-aromatic polyamide resin (A) has a structural unit composed of a dicarboxylic acid component containing terephthalic acid (TPA) and a diamine component. Examples of semi-aromatic polyamides (A) include 6T-based polyamides (for example, polyamide 6T/6I consisting of terephthalic acid/isophthalic acid/hexamethylenediamine, Polyamide 6T/66 composed of formic acid/adipic acid/hexamethylenediamine, polyamide 6T/6I/66 composed of terephthalic acid/isophthalic acid/adipic acid/hexamethylenediamine, terephthalic acid/isophthalic acid/hexamethylenediamine Polyamide 6T/M-5T composed of dicarboxylic acid/hexamethylenediamine/2-methyl-1,5-pentanediamine, polyamide composed of terephthalic acid/hexamethylenediamine/ε-caprolactam Amine 6T/6, polyamide 6T/4T composed of terephthalic acid/hexanediamine/butanediamine), 9T polyamide (terephthalic acid/1,9-nonanediamine/2-methyl) 1,8-octanediamine), 10T series polyamide (terephthalic acid/1,10-decanediamine), 12T series polyamide (terephthalic acid/1,12-dodecanediamine) amine), polyamides composed of sebacic acid/p-xylylenediamine, etc.

From the viewpoint of the melting point and the equilibrium water absorption in water, among the above-mentioned semi-aromatic polyamides, the semi-aromatic polyamide resin (A) contains 50 mol% or more of carbon number from 2 to 12 bis The structural unit obtained by the equivalent molar salt of amine and terephthalic acid, and one or more of the aminocarboxylic acid with 11 to 18 carbon atoms or the amide amine with 11 to 18 carbon atoms is copolymerized. better. The content of the constituent units obtained from the equivalent molar salt of diamine with 2-12 carbon atoms and terephthalic acid is preferably 50-98 mol %, and the amino carboxylic acid or carbon number of carbon number 11-18 is preferably 50-98 mol%. The content of one or more of the amides in the range of 11 to 18 is preferably 2 to 50 mol %.

As the diamine component having 2 to 12 carbon atoms constituting the semi-aromatic polyamide resin (A), an aliphatic diamine having 2 to 12 carbon atoms is preferable. As the aliphatic diamine component having 2 to 12 carbon atoms, 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-Methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl- 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and these may be used alone or in plural.

The melting point of the semi-aromatic polyamide resin (A) is preferably 290° C. or higher. From this viewpoint, in the case of semi-aromatic polyamides composed of structural units obtained from a molar salt of a diamine having 10 or more carbon atoms and an equivalent molar salt of terephthalic acid, the temperature may be 290°C or lower. Since it has a melting point, it contains 50 mol% or more of the structural unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and a terephthalic acid, and the melting point on the lowest temperature side is 290°C or more. Polyamide resin is the preferred aspect. When the structural unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid is less than 50 mol %, the crystallinity and mechanical properties may decrease.

In addition, in the case of semi-aromatic polyamides composed of structural units obtained from a diamine having 6 to 10 carbon atoms and an equivalent molar salt of terephthalic acid, the composition contains 55 mol% or more. The unit may be a polyamide resin having a melting point of 290° C. or higher on the lowest temperature side, which is a preferable aspect. The content of the constituent unit obtained from the equivalent molar salt of diamine with 6 to 10 carbon atoms and terephthalic acid is preferably 55 to 98 mol %, and amino carboxylic acid with 11 to 18 carbon atoms or internal The content of one or more of the amides is preferably 2-45 mol%. When the structural unit obtained from an equivalent molar salt of a diamine having 6 to 10 carbon atoms and terephthalic acid is less than 55 mol %, the crystallinity and mechanical properties may decrease.

The semi-aromatic polyamide resin (A) can copolymerize other components in a proportion of 50 mol % or less in the constituent units. As a copolymerizable diamine component, for example, 1,13-tridecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 2,2,4 (or 2 ,4,4)-Trimethylhexanediamine-like aliphatic diamines, such as piperidine, cyclohexanediamine, bis(3-methyl-4-aminohexyl)methane, bis-(4,4' -Aminocyclohexyl)methane, alicyclic diamines such as isophorone diamine, aromatic diamines such as m-xylene diamine, p-xylylene diamine, p-phenylenediamine, m-phenylenediamine, and the like hydrides, etc.

As acid components which can be copolymerized, isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphthalic acid, 2,2' -Aromatic dicarboxylic acids such as diphthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfonate isophthalic acid, 5-hydroxyisophthalic acid, fumaric acid, maleic acid, succinic acid acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,14-tetradecanedioic acid 18-Octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexane Aliphatic and alicyclic dicarboxylic acids such as dicarboxylic acid, dimer acid, and the like. Moreover, as a component which can be copolymerized, lactamides, such as ε-caprolactam, 11-aminoundecanoic acid, undecylamide, 12-aminododecanoic acid, and 12-dodecanolide, are exemplified. Amines and aminocarboxylic acids of these ring-opened structures, etc.

Among the above-mentioned components, particularly preferred copolymerization components are one or more of aminocarboxylic acids having 11 to 18 carbon atoms or lactamides having 11 to 18 carbon atoms as described above. By using aminocarboxylic acids with 11-18 carbon atoms or amides with 11-18 carbon atoms, the melting point and crystallization temperature can be adjusted to improve the formability, and the water absorption rate can be reduced to improve the physical property change and size during water absorption. For defects caused by changes, the fluidity during melting can be improved by introducing a flexible skeleton.

When a copolymerization component consists of a dicarboxylic acid and a diamine, since melting|fusing point may become less than 290 degreeC depending on a combination, it is unfavorable.

The semi-aromatic polyamide resin (A) is composed of (a) 50-99 mol % of the constituent unit obtained from an equivalent molar salt of hexamethylene diamine and terephthalic acid, and (b) 1-50 mol %. Semi-aromatic polyamide resins in which a molar % of constituent units derived from 11-aminoundecanoic acid or undecylamide are used as constituents are particularly preferred. In this case, the semi-aromatic polyamide resin (A) may contain, in addition to the structural unit of (a) and the structural unit of (b), the structural unit containing the above-mentioned copolymerizable component in a ratio of 20 mol % or less as a constituent. By using the semi-aromatic polyamide (A) composed of the constituent components, in addition to high melting point, low water absorption, and high fluidity, excellent moldability can be realized.

The semi-aromatic polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by subjecting a raw material monomer to a polycondensation reaction. The order of the polycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at the same time, or a part of the raw material monomers may be reacted first, and then the remaining raw material monomers may be reacted. In addition, the polymerization method is not particularly limited, but it may be carried out in a continuous step from charging the raw material to producing the polymer, or after producing the oligomer first, the polymerization may be carried out by an extruder or the like in another step, or the Methods such as high molecular weight oligomers by solid-phase polymerization. By adjusting the loading ratio of the raw material monomers, the ratio of each constituent unit in the synthesized copolymerized polyamide can be controlled.

As a catalyst used when manufacturing a semi-aromatic polyamide resin (A), phosphoric acid, phosphorous acid, hypophosphorous acid, or its metal salt, ammonium salt, and ester are mentioned. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. As ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester, etc. are mentioned. Moreover, it is preferable to add basic compounds, such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, from a viewpoint of improving melt retention stability.

The relative viscosity (RV) of the semi-aromatic polyamide resin (A) measured in 96% concentrated sulfuric acid at 20°C is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and further preferably 1.5 to 2.5. As a method of making the relative viscosity of polyamide into a certain range, the means of adjusting molecular weight is mentioned.

The acid value and the amine value of the semi-aromatic polyamide resin (A) are preferably 0 to 200 eq/ton and 0 to 100 eq/ton, respectively. When the terminal functional group exceeds 200 eq/ton, not only will gelation and deterioration be accelerated during melt retention, but also problems such as coloration and hydrolysis will be caused in the use environment. On the other hand, when mixing reactive compounds such as glass fiber and maleic acid-modified polyolefin, it is preferable to set the acid value and/or the amine value to be 5 to 100 eq/ton in order to blend reactivity and reactive groups.

The semi-aromatic polyamide resin (A) can adjust the amount of end groups and the molecular weight of polyamide by adjusting the molar ratio of the amount of amine groups and the amount of carboxyl groups to perform polycondensation and to add end-capping agents. When the molar ratio of the amount of amine groups to the amount of carboxyl groups is used for polycondensation at a certain ratio, the molar ratio (diamine/dicarboxylic acid) of all diamines to be used to all dicarboxylic acids (diamine/dicarboxylic acid) is adjusted to 1.00/ The range of 1.10 to 1.10/1.00 is preferable.

The timing of adding the end-capping agent includes the time when the raw material is charged, when the polymerization is started, at the later stage of the polymerization, or when the polymerization is completed. The end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amine group or carboxyl group at the end of the polyamide, and can be used: monocarboxylic acid or monoamine, acid anhydrides such as phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monohydric alcohols, etc. As the blocking agent, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, trimethylacetic acid, isomeric Aliphatic monocarboxylic acids such as butyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid, α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid , maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride and other acid anhydrides, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine Aliphatic monoamines such as ethylamine, dipropylamine, and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine, and the like.

The semi-aromatic polyamide resin (A) must be present in a proportion of 20 to 70 mass % in the entire polyamide resin composition of the present invention, preferably 25 to 55 mass %. If the ratio of the semi-aromatic polyamide resin (A) is less than the above-mentioned lower limit, the mechanical strength will be low, and if it exceeds the above-mentioned upper limit, the blending amount of other components will be insufficient, and it will become difficult to obtain the desired effect.

The halogen group-containing flame retardant (B) is blended in order to impart flame retardancy to the molded body formed from the polyamide resin of the present invention, and must contain 5 in the total polyamide resin composition of the present invention. It exists in the ratio of -15 mass %, Preferably it exists in the ratio of 7-13 mass %. As the halogen group-containing flame retardant (B), for example, tetrabromobisphenol A (TBBA), decabromodiphenyl ether (Deca-BDE), tribromophenol, hexabromocyclododecane (HBCD), Ethylene bis(tetrabromophthalimide), TBBA carbonate oligomer, TBBA epoxy oligomer, brominated polystyrene, bis(pentabromophenyl)ethane, TBBA-bis(di bromopropyl ether), hexabromobenzene (HBB). In particular, brominated polystyrene is preferable from the viewpoints of environmental safety and stability during processing. It is more preferable to use only brominated polystyrene without using other halogen-containing flame retardants in combination. The brominated polystyrene system preferably has a bromine content of 62 to 72 mass %, a weight average molecular weight of 4000 to 8000, and a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of 1.05 to 1.40. If the weight average molecular weight is less than the above range, thermal stability tends to decrease and the amount of corrosive gas generated during processing tends to increase, and if it exceeds the above range, the fluidity during injection molding tends to be poor.

The metal salt-based flame retardant auxiliary (C) is at least one metal compound selected from the group consisting of zinc stannate, zinc borate, zinc phosphate, calcium borate, and calcium molybdate, and is used for the The flame retardant (B) is combined to more highly exhibit the flame retardancy of the halogen group-containing flame retardant (B). These metal salt-based flame retardant aids are conventionally used flame retardant aids, and are those having a different action from the metal oxide (E) described later. In particular, the metal salt-based flame retardant adjuvants with zinc stannate, zinc borate, and zinc phosphate as the main components are preferable from the viewpoint of stability and the effect of the present invention.

The blending amount of the metal salt-based flame retardant auxiliary (C) in the polyamide resin composition is 0.5 to 15 mass %, preferably 1.0 to 12 mass %, and more preferably 2.0 to 10 mass %. If the blending amount of the metal salt-based flame retardant adjuvant (C) is less than the above lower limit, the target high flame retardancy cannot be obtained, and if it exceeds the above upper limit, the physical properties are greatly reduced, and the continuous productivity during mixing may be reduced. Possibility, not good.

The inorganic reinforcing material (D) is blended in order to improve the formability of the polyamide resin composition and the strength of the molded product, and it is preferable to use at least one selected from the group consisting of fibrous reinforcing materials and needle-like reinforcing materials. Examples of fibrous reinforcing materials include glass fibers, carbon fibers, boron fibers, ceramic fibers, and metal fibers, and examples of needle-like reinforcing materials include potassium titanate whiskers, aluminum borate whiskers, and zinc oxide whiskers. , calcium carbonate whiskers, magnesium sulfate whiskers, wollastonite, etc. As glass fibers, chopped strands or continuous long fibers having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, glass fibers with a circular cross-section and a non-circular cross-section can be used. The diameter of the circular cross-section glass fiber is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. In addition, from the viewpoint of physical properties and fluidity, glass fibers having a non-circular cross-section are preferable, but from the viewpoint of cost, glass fibers having a circular cross-section are preferable. The glass fibers with a non-circular cross-section also include those that are slightly elliptical, slightly oblong, and slightly cocoon-shaped in the cross-section perpendicular to the longitudinal direction of the fiber length, and the flattening ratio is preferably 1.5 to 8. . Here, the aspect ratio is assumed to be a rectangle circumscribing the smallest area of the cross-section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of the rectangle is defined as the long axis, and the length of the short side is defined as the short axis The ratio of the major diameter to the minor diameter. The thickness of the glass fiber is not particularly limited, but the short diameter is about 1 to 20 μm and the long diameter is about 2 to 100 μm. In addition, as a glass fiber, what becomes a fiber bundle and cut|disconnected into the strand shape of about 1-20 mm of fiber length can be used suitably. In addition, in order to improve the affinity with the polyamide resin, it is preferable that the fibrous reinforcing material is organically treated and treated with a coupling agent, or used in combination with a coupling agent during melt mixing. As a coupling agent, a silane-based coupling agent can be used. Any of a coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent, but among them, an aminosilane coupling agent and an epoxysilane coupling agent are particularly preferred.

In order to fully exhibit mechanical properties, the blending ratio of the inorganic reinforcing material (D) in the polyamide resin composition must be 20 to 60 mass %. The blending ratio is preferably 23 to 57% by mass, more preferably 25 to 55% by mass. If the blending ratio is less than the above-mentioned lower limit, the mechanical strength of the molded product will decrease, and if it exceeds the above-mentioned upper limit, there is a possibility that the extrudability and moldability will be reduced, which is not preferable.

The metal oxide (E) is an oxide of bismuth. The metal oxide (E) is used to promote the decomposition of the halogen group-containing flame retardant in a temperature range different from that of the metal salt-based flame retardant auxiliary (C). In combination, the decomposition of the halogen-containing flame retardant and the accompanying generation of flame retardant gas are possible in a wide range of combustion temperature, and an excellent flame retardant effect can be exhibited. On the other hand, even if the metal oxide (E) is additionally blended, the generation of halogen gas derived from the halogen group-containing flame retardant during molding is not promoted. This is because the temperature region in which the metal oxide (E) promotes the decomposition of the halogen group-containing flame retardant is higher than the temperature region in the molding process. Therefore, according to the present invention, by adding a metal oxide (E) in addition to the conventional flame retardant auxiliary, the decomposition of the halogen group-containing flame retardant during combustion is accelerated, and the flame retardant gas required during combustion is released. It is possible to produce in a wide range of combustion temperature, whereby the flame retardant effect of the halogen-based flame retardant can be fully exerted. As a result, excellent flame retardancy can be maintained even if the usage amount of the halogen group-containing flame retardant is reduced. In addition, by reducing the amount of the halogen-containing flame retardant used, the amount of undesired halogen gas generated from the halogen-containing flame retardant due to heating during molding can be reduced, and the mold can be effectively reduced. corrosion. Various metal oxides other than bismuth oxide exist as metal oxides having such an effect. However, if a metal oxide with high hardness is used, the inorganic reinforcing material will be bent more than necessary, and it is not necessary from the viewpoint of mechanical properties. Not suitable. From this viewpoint, bismuth oxide is extremely suitable.

The blending ratio of the metal oxide (E) in the polyamide resin composition must be 0.5 to 5 mass %, preferably 0.5 to 4.5 mass %, and more preferably 1 to 4 mass %. If the blending ratio is less than the above lower limit, the desired high flame retardancy cannot be obtained, and if it exceeds the above upper limit, the physical properties may be greatly reduced, and the continuous productivity during mixing may be reduced, which is unfavorable.

In addition to the components (A) to (E) described above, the polyamide resin composition of the present invention can incorporate various additives of conventional polyamide resin compositions for electrical and electronic components. Examples of additives include anti-dripping agents such as tetrafluoroethylene (PTFE), stabilizers, impact modifiers, mold release agents, slidability modifiers, colorants, plasticizers, crystal nucleating agents, and semi-aromatic The polyamide resin (A) includes polyamides having different compositions, thermoplastic resins other than polyamides, and the like. The possible compounding amounts of these components in the polyamide resin composition are as described below, but the total of these components is preferably 30 mass % or less in the polyamide resin composition, and 20 mass % % or less is more preferable, 10 mass % or less is further preferable, and 5 mass % or less is particularly preferable.

The flame-retardant polyamide resin composition of the present invention can not only have excellent flame retardancy and mold corrosion reduction, but also can suppress the combination of conventional flame retardants at a high level by adopting the above-mentioned composition. It was observed that exudates were formed on the surface of the molded product under the actual use environment, and it exhibited fluidity during molding. Furthermore, by using the semi-aromatic polyamide resin (A) which is characterized by a high melting point and a low equilibrium water absorption rate in water, in addition to a high degree of flame retardancy, a high melting point and high heat resistance can be obtained, and the water absorption can be suppressed. The flame-retardant polyamide resin composition with excellent properties such as reduced mechanical properties and dimensional change can provide products that highly meet the needs of users.

The polyamide resin composition of the present invention can be produced by blending the above-mentioned respective constituent components by a conventionally known method. For example, adding each component during the polycondensation reaction of the semi-aromatic polyamide resin (A), dry blending the semi-aromatic polyamide resin (A) and other components, or extrusion using a twin-screw screw type The method of melt-kneading each constituent component by machine.

The polyamide resin composition of the present invention can be molded by conventionally known methods such as extrusion molding, injection molding, and compression molding. Since the polyamide resin composition of the present invention hardly generates halogen gas derived from the halogen group-containing flame retardant during molding, the problem of mold corrosion does not occur. The formed molding system is excellent in heat resistance, flame retardancy, and processability, and can be used for various purposes. Specifically, various electrical and electronic components such as connectors and switches, housing components, and the like are preferable. [Example]

The present invention will be further specifically described below by means of embodiments, but the present invention is not limited to these embodiments. In addition, the measurement value described in an Example was measured by the following method.

(1) Relative viscosity 0.25 g of a polyamide resin was dissolved in 25 ml of 96% sulfuric acid, and the relative viscosity was measured at 20° C. using an Ostrich viscometer.

(2) Melting point (Tm) Using an injection molding machine EC-100 manufactured by Toshiba Machinery, the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 35°C, and a test piece for the UL combustion test with a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mmt was injection-molded. , make a test piece. In order to measure the melting point (Tm) of the obtained molded product, a part of the molded product was weighed 5 mg on an aluminum pan, sealed with an aluminum lid, and a measurement sample was prepared, and then a differential scanning calorimeter (SSC/5200 manufactured by SEIKO INSTRUMENTS) was used. ), the temperature was raised from room temperature at 20°C/min under a nitrogen atmosphere, and the measurement was performed until the melting point of the resin +30°C. At this time, the highest temperature of the peak observed on the lowest temperature side among the peaks of the endothermic peaks due to the melting was defined as the melting point (Tm).

(3) Equilibrium water absorption in water Using an injection molding machine EC-100 manufactured by Toshiba Machine Co., Ltd., the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 135°C, and a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm was injection-molded to prepare a test piece for evaluation. After the test piece was annealed in an environment of 140° C. for 2 hours, the weight was measured, and the weight at this time was defined as the weight at the time of drying. In addition, after immersing the annealed test piece in 80 degreeC hot water for 50 hours, the weight was measured, and the weight at this time was made the weight at the time of saturated water absorption. From the weights at the time of saturated water absorption and at the time of drying measured by the above-mentioned method, the equilibrium water absorption rate in water was calculated|required by the following formula. Equilibrium water absorption rate in water (%) = {(weight when saturated water absorption - weight when drying)/weight when drying}×100

(4) Tensile strength A test piece for evaluation was produced according to ISO 527-1 and 2 using an injection molding machine EC-100 manufactured by Toshiba Machine Co., Ltd., the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 135°C. Using the produced test pieces, the tensile properties were evaluated according to ISO 527-1 and 2, and the tensile strength was measured. The tensile strength was determined by the following criteria. ○: Tensile strength≧140MPa ×: Tensile strength <140MPa

(5) Tensile elongation A test piece for evaluation was produced according to ISO 527-1 and 2 using an injection molding machine EC-100 manufactured by Toshiba Machine Co., Ltd., the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 135°C. Using the produced test pieces, the tensile properties were evaluated according to ISO 527-1 and 2, and the tensile elongation was measured.

(6) Flame retardancy An evaluation test of 127mm in length, 12.7mm in width, and 0.8mm in thickness was produced by injection molding using Toshiba Machine's injection molding machine EC-100, the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 135°C. piece. Using this test piece, evaluation was performed with 10 test pieces according to the UL-94 vertical burning test. Five total burning times were calculated from the count of the number of pieces of molten droplet ignition and the burning time of the test piece without the droplets, and evaluated according to the following criteria. ○: No droplet ignition occurred, and the total burning time of the five pieces was 50 seconds or less. ×: Droplet ignition occurred, or the total burning time of 5 pieces was longer than 50 seconds.

(7) Mold corrosion resistance Place 10g resin pellets on the aluminum foil in the range of φ900mm, load a glass plate with a thickness of 20mm × 50mm × 2mm on the top of the particles, load a copper plate with a thickness of 10mm × 30mm × 1mm on it, and cover the lid of a φ900mm glass petri dish . After heat-processing this on a 330 degreeC hotplate for 15 minutes, the surface state of a copper plate was visually observed, and it evaluated based on the following judgment criteria. ○: No corrosion. There is no discoloration of the copper plate and almost no deposits. △: Slightly corroded. The copper plate was discolored to blue, and it was in a state of a small amount of deposits. ×: Corrosion occurred. The copper plate was discolored to brown, and it was in a state of a large amount of deposits.

(8) MI (melt flow index) According to ISO1133, the cylinder temperature was set to 330° C., and the load was set to 2.16 kg, and the fluidity evaluation was carried out.

(9) Exudation resistance Using an injection molding machine EC-100 manufactured by Toshiba Machinery, the cylinder temperature was set to the melting point of the resin + 20°C, and the mold temperature was set to 135°C, and a flat plate of length 100 × width 100 × thickness 1 mm was injection-molded to prepare a test piece for evaluation. After the test piece for evaluation was left to stand for 200 hours in an environment of 80° C. 85% RH (relative humidity), the generation state of the exudate on the surface of the test piece was visually confirmed by the following criteria. ○: No exudate was produced. ×: Exudate was produced.

Synthesis of Semi-aromatic Polyamide Resin (A) The following two types of semi-aromatic polyamide resins (A-1) and (A-2) were synthesized as semi-aromatic polyamide resins (A) used in Examples and Comparative Examples.

<Semi-aromatic polyamide resin (A-1) synthesis> 7.54 kg of 1,6-hexanediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, and hypophosphorous acid as a catalyst 9 g of sodium, 40 g of acetic acid as a terminal adjuster, and 17.52 kg of ion-exchanged water were charged into a 50-liter autoclave, _{pressurized from normal pressure to 0.05 MPa with N 2} , released and returned to normal pressure. This operation was performed three times, and after N ₂ substitution was performed, it was uniformly dissolved under stirring at 135° C. and 0.3 MPa. After that, the dissolved liquid was continuously supplied by the liquid feeding pump, and the temperature was raised to 240° C. with the heating pipe, and heated for 1 hour. Then, the reaction mixture was supplied to a pressurized reaction tank, heated at 290° C., and a part of water was distilled off so that the tank internal pressure was maintained at 3 MPa to obtain a low-order condensate. Thereafter, the low-order condensate was supplied to a direct biaxial extruder (screw diameter 37 mm, L/D=60) maintained in a molten state, the resin temperature was set to 335° C., and water was removed from the three vent holes. Polycondensation was performed under melting to obtain semi-aromatic polyamide resin (A-1). The obtained semi-aromatic polyamide resin (A-1) has a relative viscosity of 2.02, a melting point of 315° C., an acid value of 126 eq/ton, and an amine value of 22 eq/ton.

<Semi-aromatic polyamide resin (A-2) synthesis> 7.54 kg of 1,6-hexanediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, and hypophosphorous acid as a catalyst 9 g of sodium, 15 g of acetic acid as a terminal regulator, and 17.52 kg of ion-exchanged water were charged into a 50-liter autoclave, _{pressurized from normal pressure to 0.05 MPa with N 2} , released and returned to normal pressure. This operation was performed three times, and after N ₂ substitution was performed, it was uniformly dissolved under stirring at 135° C. and 0.3 MPa. After that, the dissolved liquid was continuously supplied by the liquid feeding pump, and the temperature was raised to 240° C. with the heating pipe, and heated for 1 hour. Then, the reaction mixture was supplied to a pressurized reaction tank, heated at 290° C., and a part of water was distilled off so that the tank internal pressure was maintained at 3 MPa to obtain a low-order condensate. Thereafter, the low-order condensate was supplied to a direct biaxial extruder (screw diameter 37 mm, L/D=60) maintained in a molten state, the resin temperature was set to 335° C., and water was removed from the three vent holes. Polycondensation was performed under melting to obtain semi-aromatic polyamide resin (A-2). The obtained semi-aromatic polyamide resin (A-2) has a relative viscosity of 2.48, a melting point of 315° C., an acid value of 98eq/ton, and an amine value of 34eq/ton.

Examples 1 to 9, Comparative Examples 1 to 9 The components and mass ratios (parts by mass) described in Table 1 were melted at the melting point of each semi-aromatic polyamide resin raw material + 20°C under the following conditions using a 2-axis extruder TEM26SS manufactured by Toshiba Machine Co., Ltd. Kneading was performed to obtain the polyamide resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9. Using the polyamide resin composition of each Example and Comparative Example, performance evaluation was performed by the above-mentioned method. The results are shown in Table 1. Mixing conditions: screw speed 200rpm Spit volume 20kg/h Glass fiber (GF) is fed from the side feeder, and other raw materials are fed from the main feeder (MF).

In addition, the details of each component described in Table 1 are as follows. Semi-aromatic polyamide resin (A) ・Semi-aromatic polyamide resin (A-1) (PA6T/11 (polyamide 6T/11), melting point: 315℃, relative viscosity: 2.02, acid value 126eq/ ton, amine value 22eq/ton) ・Semi-aromatic polyamide resin (A-2) (PA6T/11 (polyamide 6T/11), melting point: 315℃, relative viscosity: 2.48, acid value 98eq/ton, Amine value: 34eq/ton) Halogen-containing flame retardant (B) ・Brominated polystyrene (SAYTEX (registered trademark) HP-3010PST manufactured by Albemarle Corporation, bromine content 68%, Mw: 5100, Mn: 4500, Mw/ Mn: 1.14 (polystyrene conversion)) Metal salt-based flame retardant aid (C) ・Zinc stannate (FLAMART S (registered trademark) manufactured by Nippon Light Metal Corporation) Inorganic reinforcing material (D) ・Glass fiber (Nihon Electric Glass ( Co., Ltd., T-275H, circular cross section) Metal oxide (E) ・Bismuth oxide (Bi ₂ O ₃ ) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.) ・ Alumina (Al ₂ O ₃ ) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.) ・Titanium oxide (TiO ₂ ) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.) ・Iron oxide (Fe ₂ O ₃ ) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.)・Zinc oxide (ZnO) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.) ・Tin oxide (SnO ₂ ) (Wako 1st grade, Wako Pure Chemical Industries, Ltd.) Additives ・Anti-dripping agent: Polytetrafluoroethylene (Daikin POLYFLON MPA (registered trademark) FA500H manufactured by Kogyo Co., Ltd. ・Talc (KCM7500 manufactured by Hayashi Kasei Co., Ltd., particle size 5.8 μm) ・Mold release agent: Octacosate (LICOLUB (registered trademark) WE40 manufactured by Clariant Corporation) ・Stabilizer: 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4 ,8,10-Tetraspiro[5.5]undecane (ADK STAB (registered trademark) AO-80 manufactured by ADEKA Corporation)

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Element semi-aromatic (A-1) 44 45 42 0 47 33 27 40 twenty two Polyamide resin (A) (A-2) 0 0 0 44 0 0 0 0 twenty two Halogen-based flame retardant (B) Brominated Polystyrene 12 12 12 12 14 10 8 12 12 Metal salt flame retardant additives (C) Zinc stannate 4 4 4 4 4 3 3 8 4 Inorganic reinforcement (D) glass fiber 35 35 35 35 30 50 55 35 35 Metal oxide (E) Bismuth oxide 2 1 4 2 2 1 4 2 2 Alumina 0 0 0 0 0 0 0 0 0 Titanium oxide 0 0 0 0 0 0 0 0 0 Iron oxide 0 0 0 0 0 0 0 0 0 Zinc oxide 0 0 0 0 0 0 0 0 0 Tin oxide 0 0 0 0 0 0 0 0 0 additive Anti-dripping agent 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 talc 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 release agent 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 stabilizer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total (mass %) 100 100 100 100 100 100 100 100 100 Evaluation Melting point(℃) 315 315 315 315 315 315 315 315 315 Equilibrium water absorption in water (%) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Tensile strength (MPa) ○ 160 ○ 160 ○ 155 ○ 170 ○ 150 ○ 170 ○ 170 ○ 140 ○ 165 Tensile elongation (%) 1.5 1.5 1.4 1.6 1.3 1.7 1.6 1.2 1.6 flame retardancy 5 total burning time (s)* 25 33 30 26 28 34 44 26 twenty three Whether there is resistance to dripping fire none none none none none none none none none Overview ○ ○ ○ ○ ○ ○ ○ ○ ○ Mold corrosion resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ MI(g/10min) 2.16kgf 32 30 36 20 38 12 10 25 26 Exudation resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ *No droplet conversion value Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Element semi-aromatic (A-1) 39 46 40 44 44 44 44 44 48 Polyamide resin (A) (A-2) 0 0 0 0 0 0 0 0 0 Halogen-based flame retardant (B) Brominated Polystyrene 18 12 12 12 12 12 12 12 12 Metal salt flame retardant additives (C) Zinc stannate 5 4 4 4 4 4 4 4 0 Inorganic reinforcement (D) glass fiber 35 35 35 35 35 35 35 35 35 Metal oxide (E) Bismuth oxide 0 0 6 0 0 0 0 0 2 Alumina 0 0 0 2 0 0 0 0 0 Titanium oxide 0 0 0 0 2 0 0 0 0 Iron oxide 0 0 0 0 0 2 0 0 0 Zinc oxide 0 0 0 0 0 0 2 0 0 Tin oxide 0 0 0 0 0 0 0 2 0 additive Anti-dripping agent 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 talc 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 release agent 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 stabilizer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total (mass %) 100 100 100 100 100 100 100 100 100 Evaluation Melting point(℃) 315 315 315 315 315 315 315 315 315 Equilibrium water absorption in water (%) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Tensile strength (MPa) ○ 155 ○ 160 ○ 145 × 135 × 130 ○ 150 ○ 150 ○ 150 ○ 165 Tensile elongation (%) 1.4 1.5 1.3 1.2 1.2 1.4 1.4 1.4 1.6 flame retardancy 5 total burning time (s)* 20 55 40 35 40 33 49 45 60 Whether there is resistance to dripping fire none have have have have have have have have Overview ○ × × × × × × × × Mold corrosion resistance × ○ ○ ○ ○ ○ Δ Δ ○ MI(g/10min) 2.16kgf 30 28 40 28 33 35 31 32 33 Exudation resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ *No droplet conversion value

As shown in Table 1, Examples 1 to 9 satisfying all the requirements of the present invention all have high heat resistance (melting point) and high flame retardancy, and reduce mold corrosion. On the other hand, Comparative Example 1 is an example in which the blending amount of the halogen group-containing flame retardant (B) is increased more than that of Example 1 without blending the metal oxide (E). Although the flame retardancy is excellent, the mold Corrosion resistance is poor. Comparative Example 2 is an example in which the blending amount of the halogen group-containing flame retardant (B) is the same as that of Example 1, but the metal oxide (E) is not blended. Although the mold corrosion resistance is excellent, the flame retardancy is inferior. Comparative Example 3 is an example in which the blending amount of the metal oxide (E) is too large, and since the resin viscosity becomes too small, a droplet behavior occurs during combustion, and the flame retardancy is inferior. Comparative Examples 4 to 8 are examples using those other than the specific metal oxides specified in the present invention as the metal oxides (E), and all of them have poor flame retardancy. In addition, the mechanical properties of the Comparative Examples 4 and 5 series were also inferior. Comparative Example 9 is an example in which the metal salt-based flame retardant auxiliary (C) is not blended with the conventional flame retardant auxiliary, and only the halogen group-containing flame retardant (B) and the metal oxide (E) are used in combination, and the flame retardancy inferior. [Industrial Availability]

The flame-retardant polyamide resin composition of the present invention has high heat resistance, and by using a specific metal oxide in addition to the conventional flame-retardant auxiliary agent, it can maintain excellent flame retardancy and reduce flame retardancy containing halogen groups. dosage of the agent. Therefore, the amount of halogen gas generated from the halogen-based flame retardant during molding can be reduced, and mold corrosion can be reduced. Furthermore, it has excellent fluidity during molding, can suppress the generation of exudates on the surface of molded articles under actual use environments such as high temperature and humidity, and can also reduce strength reduction and dimensional changes due to water absorption by polyamide resins. Therefore, according to the present invention, a molded article highly satisfying the user's needs can be manufactured industrially advantageously.

Claims (8)

A flame-retardant polyamide resin composition, characterized in that it contains half a Aromatic polyamide resin (A), halogen group-containing flame retardant (B), at least one metal selected from the group consisting of zinc stannate, zinc borate, zinc phosphate, calcium borate, and calcium molybdate Salt-based flame retardant auxiliary (C), inorganic reinforcing material (D), and metal oxide (E) composed of bismuth oxide. The flame-retardant polyamide resin composition of claim 1, wherein the semi-aromatic polyamide resin (A) contains more than 50 mol% of diamines with 2 to 12 carbon atoms, terephthalic acid, etc. The structural unit obtained by measuring the molar salt is obtained by copolymerizing one or more of aminocarboxylic acids with 11 to 18 carbon atoms or amides with 11 to 18 carbon atoms. The flame-retardant polyamide resin composition of claim 1 or 2, wherein the semi-aromatic polyamide resin (A) is a mixture of (a) 50-99 mol% of hexamethylenediamine and terephthalic acid. The constituent unit obtained from an equivalent molar salt and (b) 1 to 50 mol % of the constituent unit obtained from 11-aminoundecanoic acid or undecylamide are used as constituent components. The flame-retardant polyamide resin composition of claim 1 or 2, wherein the halogen-containing flame retardant (B) is brominated polystyrene. The flame-retardant polyamide resin composition of claim 4, wherein the bromine content of the brominated polystyrene is 62-72% by mass, the weight-average molecular weight is 4,000-8,000, and the molecular weight distribution (weight-average molecular weight (Mw)/ The number average molecular weight (Mn) is 1.05 to 1.40. The flame-retardant polyamide resin composition according to claim 1 or 2, wherein the inorganic reinforcing material (D) is glass fiber. An electrical and electronic component characterized by being formed using the flame-retardant polyamide resin composition according to any one of claims 1 to 6. A housing member characterized by being formed using the flame-retardant polyamide resin composition according to any one of claims 1 to 6.