TW201336932A - Flame retardant polyamide resin composition and molded article made thereof - Google Patents

Abstract

To provide a flame retardant polyamide resin composition and a molded article made thereof which can have great formability, and excellent glow wire property, flame retardancy, electrical characteristics. The flame retardant polyamide resin composition of the present invention comprises a polyamide resin (A), a triazine-based compound (B), and a lubricant (C). In the blending ratio of the polyamide resin (A), the triazine-based compound (B) and lubricant (C), with respect to the polyamide resin (A) of 100 parts by mass, the triazine-based compound is 12 to 38 parts by mass, the lubricant (C) is 0.1 to 2.0 parts by mass. The lubricant (C) comprises a higher fatty acid metal salt (C1) and a carboxylic amide-based wax (C2) with a mass ratio of (C1) / (C2) = 30 / 70 to 70 / 30.

Description

Flame retardant polyamide resin composition and molded article composed thereof

The present invention relates to a flame retardant polyamide resin composition which is excellent in moldability, glow wire characteristics, flame retardancy, and electrical properties, and a molded article comprising the same.

In the past, polyamine resins have been widely used in housings, exterior parts, and electrical fields because of their excellent mechanical properties, heat resistance, flame retardancy, electrical properties, and moldability, especially in connector applications. Missing resin. However, in recent years, as the size of the product has been reduced, the frame, the exterior parts, and the connector have been required to be further reduced in size and thickness. Therefore, the requirements for the flame retardancy of the resin have become stricter, and the height is required. Incombustible technology. Among them, the ignition wire ignition temperature is based on the revision of IEC60335-1 ("Safety of electric machines for household and similar purposes"), and the required temperature is changed from 725 °C to 775 °C, and the product is not used. The thickness was tested and the thickness closest to the thickness of the article was tested. Moreover, the anti-leakage index specified by IEC 60112 is often used as an index of electrical characteristics, and the requirement is 600 V or more.

As a technique for improving flame retardancy and electrical properties, for example, a polyamine composed of a salt of an aliphatic diamine and an aliphatic dicarboxylic acid in a predetermined ratio (a) and an indoleamine have been disclosed. Or polyamine composed of ω-amino acid constitutes unit (b) 100 parts by weight of polyamine resin obtained by polymerization, blending three A flame retardant polyamide resin composition having a flame retardant of 35 to 60 parts by weight (see, for example, Patent Document 1). However, the polyamide resin composition of Patent Document 1 is excessively blended by three Since it is a flame retardant, there is a fear that the toughness of the molded article is lowered, and the formability is also problematic in the case of molding a product having a complicated shape. Moreover, although a dispersing agent containing a higher fatty acid salt and a carboxylic acid amide amine wax in a predetermined ratio is added in order to improve moldability, it is difficult to combine both formability and glow wire characteristics.

Further, a flame retardant polyamide resin composition containing 10 to 60 parts by weight of an amine group based on 100 parts by weight of the polyamide resin has been disclosed. The salt of the compound and at least one compound selected from the group consisting of a hindered phenol compound, a hydrotalcite, and a hydroxide of an alkaline earth metal (for example, refer to Patent Document 2). Patent Document 2 describes the selection of an amine group III as a flame retardant The salt of the compound is blended with about 10 parts by weight based on 100 parts by weight of the polyamide resin to exhibit an effect of flame retardancy, glow silk, and the like. However, the examples thereof only confirmed the effect of the polyamine resin composition obtained by blending 40 parts by weight of a flame retardant, and the polyamide resin composition containing about 40 parts by weight of a flame retardant may cause a molded article. The toughness is lowered, and there is a problem of formability in the case of forming a product having a complicated shape.

Furthermore, it has been disclosed that it contains polyamine resin, three A flame retardant polyamine resin which is a flame retardant and a carboxylic acid amide amine wax (see, for example, Patent Document 3). Patent Document 3 discloses a technique in which a carboxylic acid amide-based wax used as a lubricant is used to impart good formability, but even the polyamide resin composition of Patent Document 3 has a more complicated shape in forming. It is also difficult to combine both formability and glow wire properties on the product.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2008-239896

Patent Document 2 US Patent Application Publication No. 2010/160501

Patent Document 3 European Patent Application Publication No. 1533343

In view of the above-described problems of the prior art, the present invention provides a flame retardant polyamide resin composition which is excellent in moldability and has excellent glow wire properties, flame retardancy, electrical properties and toughness. The molded article is a problem.

The inventors of the present invention conducted an intensive review to solve the above problems, and as a result, found that by using a specific amount The flame retardant polyamine resin composition obtained by blending the compound (B), the higher fatty acid metal salt (C1), and the carboxylic acid amide amine wax (C2) with the polyamide resin (A) can achieve the above purpose. The present invention has been completed.

That is, the flame retardant polyamide resin composition of the present invention contains a polyamide resin (A), three Compound (B), and lubricant (C), the above polyamine resin (A), the aforementioned three The blending ratio of the compound (B) and the lubricant (C) is the above three with respect to 100 parts by mass of the polyamide resin (A). The compound (B) is 12 to 38 parts by mass, the lubricant (C) is 0.1 to 2.0 parts by mass, and the lubricant (C) contains (C1) / (C2) = 30/70 to 70/30 by mass. Higher fatty acid metal salt (C1) and carboxylic acid amide amine wax (C2).

Furthermore, in the above-mentioned invention, the polyamidamide resin (A) is a hexamethyleneamine unit (a1) and 2 which are contained in an amount of at least 2% by mass to 98% by mass. Polyamine 6/polyamine 66 copolymerized resin (A1) of hexamethylene adipamide unit (a2) having a mass% or more and 98% by mass or less.

Further, in the above-described invention, the polyacetamide resin (A) is a hexamethyleneamine unit (a1) and 2 containing at least 50% by mass to 98% by mass or less. Polyamine 6/polyamine 66 copolymerized resin (A2) of hexamethylene adipamide unit (a2) having a mass% or more and 50% by mass or less.

Further, in the flame retardant polyamide resin composition of the present invention, in the above invention, the polyamide resin (A) further comprises at least more than 50% by mass and 98% by mass or less of hexamethylene hexane. A polyamide amine 66/polyamine 6 copolymerized resin (A3) having a guanamine unit (a2) and 2% by mass or more and less than 50% by mass of hexamethyleneamine unit (a1).

Further, in the flame-retardant polyamine resin composition of the present invention, in the above invention, the polyamine 6/polyamine 66 copolymer resin (A2) and the polyamide 66/polyamine 6 copolymer resin ( The mass ratio of A3) is (A2)/(A3)=15/85~85/15.

Further, in the flame-retardant polyamide resin composition of the present invention, in the above invention, the polyamide resin (A) further contains a polyamide 66 resin (A4).

Further, in the above-described invention, the flame retardant polyamide resin composition of the present invention is obtained by injection molding the flame retardant polyamide resin composition under the conditions of a drum temperature of 280 ° C and a mold surface temperature of 80 ° C. It Each test piece having a thickness of 0.75 mm, 1.5 mm, and 3 mm was subjected to a glow wire ignition temperature of 825 ° C or higher in accordance with the test of IEC 60695-2-13.

Moreover, the molded article of the present invention is obtained by molding the flame retardant polyamide resin composition of any one of the above items by injection molding, extrusion molding or blow molding.

Further, in the molded article of the present invention, in the above invention, the molded article is a frame, an exterior component or a connector.

The flame retardant polyamide resin composition of the present invention is obtained by a specific amount of three The compound (B), the higher fatty acid metal salt (C1) as the lubricant (C), and the amide amine wax (C2) are blended in the polyamide resin (A) to maintain high flame retardancy and toughness. , excellent glow wire characteristics and electrical properties, and have good formability.

Form of implementing the invention

Hereinafter, embodiments of the present invention will be described.

The polyamidamine resin (A) used in the present invention may, for example, be an internal amine of 3 or more rings, a polymerizable amino acid, a diamine and a dibasic acid, or a polymer obtained by polymerizing these mixtures. Amidoxime resin.

Specific examples thereof include polydecylamine resins derived from decylamine such as ε-caprolactam, heptanoin, decanoate, and caprolactam, and amine groups. Acid, 7-aminoheptanoic acid, 8-aminooctane octanoic acid, 9-amino decanoic acid, 10-amino decanoic acid, 11-aminoundecanoic acid, 12-aminododecane oxime A polyamine resin obtained from a polymerizable amino acid such as an acid.

Further, the polyamine resin obtained from a diamine and a dibasic acid may be selected from the group consisting of tetramethylene diamine, pentamethylenediamine, and 2-methyl-1,5-diamino group. Pentane, 3-methyl-1,5-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylene Amine, undecyldiamine, dodecamethylenediamine, o-xylenediamine, m-xylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, a diamine such as 1,3-diaminocyclohexane or 1,4-diaminocyclohexane; selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and , 7-heptanedicarboxylic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, p-nonanoic acid, isodecanoic acid, A polydecylamine resin obtained by dicarboxylic acid such as citric acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid.

Alternatively, the polyamine resin (A) used in the present invention may, for example, be any copolymer of the above monomer units. Further, the polyamide resin (A) may contain two or more kinds of the above polyamine resin or polyamine copolymer.

The polyamine resin (A) used in the present invention is preferably a polyamide-6/polyamine 66 copolymerized resin from the viewpoint of toughness, moldability, and cost of the molded article. In particular, the polyamine resin (A) used in the present invention preferably contains at least 2% by mass to 98% by mass of hexamethyleneamine unit (a1) and 2% by mass or more and 98% by mass or less of hexamethylene. Polyamide 6/polyamine 66 copolymerized resin (A1) of hexamethylenediamine unit (a2). By using the copolymerized polyamine resin, the glow wire characteristics and the enthalpy properties of the molded article can be further improved.

The polyamidamine resin (A) used in the present invention preferably contains at least 50% by mass to 98% by mass of hexamethyleneamine units (a1) and 2 Polyamine 6/polyamine 66 copolymerized resin (A2) of hexamethylene adipamide unit (a2) having a mass% or more and 50% by mass or less. The polyamidamide resin (A) used in the present invention is particularly preferably at least 70% by mass to 98% by mass of hexamethyleneamine unit (a1) and 2% by mass or more and 30% by mass or less of hexamethylene hexane. The copolymer of the guanamine unit (a2) is preferably at least 90% by mass to 98% by mass of hexamethyleneamine unit (a1) and 2% by mass or more and 10% by mass or less of hexamethylene hexanediamine unit. Copolymer of (a2).

The polyamidamide resin (A) which is related to the present invention, by using a polyamidoamine 6/polyamine 66 copolymerized resin (A2) containing 50% by mass or more of hexamethyleneamine unit (a1), even in a large amount Blending three In the case of the compound (B), the toughness of the molded article can be highly maintained, and the appearance is good. Further, by using a polyamine 6/polyamine 66 copolymerized resin (A2) containing 2% by mass or more of hexamethylene hexamethylenediamine unit (a2), the glow wire characteristics of the molded article can be made more Upgrade.

Further, the polyamide resin (A) according to the present invention preferably comprises a polyamide-6/polyamine 66 copolymer resin (A2) and at least more than 50% by mass and 98% by mass or less. The hexamethylene hexamethyleneamine unit (a2) and the polyamine 66/polyamine 6 copolymerized resin (A3) having 2% by mass or more and less than 50% by mass of the hexamethyleneamine unit (a1). Copolymerization resin (A3) with polyamido 66/polyamine 6 by copolymerization of polyamine 6/polyamine 66 copolymer resin (A2), even in a large amount of three In the case of the compound (B), the toughness at the time of water absorption of the molded article can be maintained at a high level, and the appearance of the molded article is good. The polyamido 6/polyamine 66 copolymerized resin (A2) and the polyamide-6/polyamine 6 copolymerized resin (A3) are used in combination, and particularly preferably at least 70% by mass to 98% by mass of the six Asians. a copolymer of methyl hexamethyleneamine unit (a2) and 2% by mass or more and 30% by mass or less of hexamethyleneamine unit (a1), preferably at least 90% by mass to 98% by mass of hexamethylene hexa A copolymer of diammonium unit (a2) and 2% by mass or more and 10% by mass or less of hexamethyleneamine unit (a1).

As the polyamine resin (A) related to the present invention, a polyamido 66/polyamine 6 copolymerized resin (A3) containing 2% by mass or more of hexamethyleneamine unit (a1) and polyamine 6/polyamine 66 copolymerized resin (A2) and used even in a large amount of blending three In the case of the compound (B), the toughness of the molded article can be maintained at a high level, and the appearance is good. Further, by using a polyamido 66/polyamine 6 copolymerized resin (A3) containing more than 50% by mass of hexamethylene adipamide unit (a2) and polyamine 6/polyamine 66 The copolymerized resin (A2) is used in combination to further improve the glow wire characteristics of the molded article.

In addition, the content ratio of the polyamide (6) and the polyamine 66/polyamine 6 copolymer (A3) is not particularly limited, and the toughness of the molded article is further improved. The improvement is preferably (A2)/(A3)=15/85~85/15 (mass ratio), and further preferably (A2)/(A3)=20/80~80/20 (mass ratio) . The polyamine resin (A) according to the present invention contains (A2) and (A3) in an amount of 15% by mass or more, respectively, and the toughness at the time of water absorption of the molded article can be highly maintained.

Further, the polyamide resin (A) according to the present invention preferably further contains a polyamide amine 66 resin (A4). The polyamide resin (A) according to the present invention contains a polyamide amine 66 resin (A4), so that the moldability, such as the release property, is greatly improved without impairing the glow wire characteristics. Preferably, polyamido 6/polyamine 66 copolymerized resin (A2) and polyamine 66 resin are used in combination. (A4). The content of the polyamido 66 resin (A4) in the polyamide resin (A) is not particularly limited, and from the viewpoint of improving the moldability, it is preferred that the polyamide resin (A) contains 10 Polyamine 66 resin (A4) having a mass % or more.

The molecular weight of the polyamide resin (A) used in the present invention is not particularly limited, and it is preferably dissolved at a concentration of 1 g/dl from the viewpoint of fluidity of the resulting flame retardant polyamide resin composition. The relative viscosity of the solution in 98% concentrated sulfuric acid is in the range of 1.8 to 5.0 at 25 ° C, preferably in the range of 1.8 to 4.0.

The method for producing the polyamide resin (A) used in the present invention is not particularly limited. For example, the above-described three-membered ring or higher in the polymerization tank can be polymerized in a polymerization tank at a high temperature. The amino acid, the diamine and the dibasic acid, or a mixture thereof, are condensed to form an oligomer, and then the desired polymerization is obtained by subjecting the polymerization to an appropriate melt viscosity by depressurization. Indoleamine resin (A). Of course, commercial products can also be used.

The flame retardant polyamide resin composition of the present invention must be three with respect to 100 parts by mass of the polyamide resin (A). The compound (B) is in a ratio of 12 to 38 parts by mass and contains a polyamide resin (A) and three Compound (B). The flame retardant polyamine resin composition of the present invention contains three Since the compound (B) is obtained, a molded article containing high glow wire properties and flame retardancy can be obtained. In the flame retardant polyamide resin composition of the present invention, in the third When the content of the compound (B) is less than 12 parts by mass, the glow wire characteristics of the molded article are lowered. three The content of the compound (B) is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. On the other hand, in the flame retardant polyamide resin composition of the present invention, three When the content of the compound (B) exceeds 38 parts by mass, the toughness of the molded article is lowered. three The content of the compound (B) is preferably 33 parts by mass or less.

In the present invention, three Compound (B) refers to a compound containing three nitrogen atoms and having an unsaturated 6-membered ring structure. Skeletal compound. three The compound (B) is known as a flame retardant which is blended with a thermoplastic resin to impart flame retardancy. Specific examples thereof include melamine, melem, melam, melamine, and cyanuric acid, and melamine, melem, melam or melamine and trimer. a salt of cyanate. Also, a mixture of these may be used. From the viewpoints of heat resistance and miscibility with the polyamide resin (A), a particularly preferred one is melamine cyanurate. three The average particle diameter of the compound (B) is preferably 15 μm or less. When the average particle diameter is 15 μm or less, the toughness at the time of water absorption can be further improved. Further, the average particle diameter is a number average particle diameter calculated from a value measured in accordance with JIS K 5600-9-3 (2006).

three For the compound (B), for example, MC25 (melamine cyanurate) manufactured by Italmatch Co., Ltd., MC4000 (melamine cyanurate) manufactured by Nissan Chemical Industries Co., Ltd., or the like can be used.

The lubricant (C) used in the present invention can contain a higher fatty acid metal salt (C1) and a carboxylic acid amide amine wax (C2) from the viewpoint of glow wire characteristics and moldability. In the flame retardant polyamide resin composition of the present invention, by using a higher fatty acid metal salt (C1) and a carboxylic acid amide amine wax (C2) in combination, it is possible to have both excellent glow wire characteristics and formability. In the present invention, it is important to contain it in a mass ratio of (C1) / (C2) = 30 / 70 to 70 / 30. Relative to the total amount of (C1) and (C2), at (C1) is less than 30% by mass and (C2) is super When it is 70% by mass, the glow wire characteristics of the molded article are lowered. On the other hand, when (C1) exceeds 70% by mass and (C2) is less than 30% by mass, moldability is lowered. Further, from the viewpoint of improving moldability, the content ratio of the higher fatty acid metal salt (C1) to the carboxylic acid amide amine wax (C2) is preferably (C1) / (C2) = 35 / 65 - 65 /35, the best one is (C1)/(C2)=40/60~60/40. By using the higher fatty acid metal salt (C1) and the carboxylic acid amide amine wax (C2) in the above content ratio, the formability of the flame retardant polyamide resin composition of the present invention can be greatly improved, and the moldability can be easily improved. A molded article having a thinner and complicated shape is obtained.

Moreover, in the flame retardant polyamide resin composition of the present invention, it is important that the total amount of the lubricant (C) is 0.1 to 2.0 parts by mass based on 100 parts by mass of the polyamide resin (A). In the flame retardant polyamide resin composition of the present invention, when the total amount of the lubricant (C) is less than 0.1 part by mass, the formability is lowered. It is preferably 0.5 parts by mass or more. On the other hand, when the total amount of (C) exceeds 2.0 parts by mass, the glow wire characteristics of the molded article are lowered. It is preferably 1.9 parts by mass or less.

The higher fatty acid metal salt (C1) used in the present invention is an aliphatic carboxylic acid having a carbon number of 12 or more or a salt of a hydroxycarboxylic acid and a metal ion, specifically, lauric acid, myristic acid, palmitic acid, or stearic acid. , eucalyptus acid, wax acid, montanic acid, melonic acid, oleic acid, erucic acid, 12-hydroxystearic acid, etc., aliphatic carboxylic acid or hydroxycarboxylic acid and lithium, calcium, barium, magnesium, aluminum, zinc, etc. A salt of a metal ion. As the higher fatty acid metal salt (C1), two or more of these may be used. In particular, from the viewpoint of price and versatility, lithium stearate and calcium stearate are preferred, and lithium stearate is preferred.

As the higher fatty acid metal salt (C1), for example, Li-St (lithium stearate) manufactured by Shengtian Chemical Co., Ltd., or the like can be used.

The carboxylic acid amide amine wax (C2) used in the present invention is a compound obtained by polycondensing an aliphatic carboxylic acid, a hydroxycarboxylic acid, and/or a polybasic acid with a diamine. Examples of the aliphatic carboxylic acid or hydroxycarboxylic acid used in the carboxylic acid amide amine wax (C2) include lauric acid, myristic acid, palmitic acid, stearic acid, eucaly, wax, and montanic acid. Bee fuliginic acid, oleic acid, erucic acid, 12-hydroxystearic acid.

Further, examples of the polybasic acid used in the carboxylic acid amide amine wax (C2) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, and sebacic acid. 1,10-decanedicarboxylic acid, citric acid, p-nonanoic acid, cyclohexanedicarboxylic acid, cyclohexyl succinic acid.

On the other hand, examples of the diamine used in the carboxylic acid amide amine wax (C2) include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, and hexamethylenediamine. M-xylylenediamine, toluenediamine, p-xylylenediamine, phenylenediamine, isophoronediamine, 1,10-nonanediamine, 1,12-dodecanediamine, 4, 4-Diaminodicyclohexylmethane, 4,4-diaminodiphenylmethane.

The carboxylic acid amide amine wax (C2) used in the present invention may, for example, be a polycondensation compound of the above aliphatic carboxylic acid, hydroxycarboxylic acid, and/or polybasic acid and diamine. As the carboxylic acid amide amine wax (C2) used in the present invention, two or more kinds of these may be used. In particular, from the viewpoint of general versatility, a compound obtained by polycondensing stearic acid, sebacic acid, and ethylenediamine is preferred.

The carboxylic acid amide amine wax (C2) can be, for example, manufactured by Kyoeisha Chemical Co., Ltd.: WH215 (polycondensate of ethylenediamine and sebacic acid, stearic acid).

The flame retardant polyamide resin composition of the present invention may further contain one or more other polymers, a copper-based heat stabilizer, a hindered phenol system, a phosphorus system, or a sulfur system, within the range not impairing the object of the present invention. Ordinary additives such as antioxidants, thermal stabilizers, ultraviolet absorbers, antistatic agents, and coloring agents containing dyes and pigments.

The method for producing the flame retardant polyamine resin composition of the present invention is not particularly limited, and examples thereof include a kneader using a uniaxial or 2-axis extruder and a kneader, and a temperature of 220 ° C to 330 ° C. A method of melt-kneading a mixture of the above materials. Again, three The flame retardant such as the compound (B) has a higher flame retardancy in order to exhibit dispersibility, and is preferably a method of melt-kneading together with the polyamide resin (A) component.

According to the flame retardant polyamide resin composition of the present invention, a molded article having excellent glow wire characteristics can be obtained. Specifically, in the test based on IEC60695-2-13 at the time of injection molding under the conditions of a drum temperature of 280 ° C and a mold surface temperature of 80 ° C, it is preferable that the glow wire ignition temperature is 0.75 mm and 1.5 mm in thickness. 3mm is 825 ° C or more. If the glow wire ignition temperature is above 825 °C, it can further improve the glow wire characteristics of complex product shapes. The glow wire ignition temperature is called GW-IT (Glow Wire Ignition Temperature), and the temperature at which the wire is heated to a desired temperature is pressed against a resin molded article having a predetermined thickness, and the maximum temperature at which the fire is extinguished within 5 seconds after ignition or ignition +25 ° C (where the test temperature is 900 to 960 ° C, the maximum temperature + 30 ° C).

The flame retardant polyamide resin composition of the present invention can be easily molded by a general method such as injection molding, extrusion molding, or blow molding, and the obtained molded article has excellent moldability, glow wire characteristics, toughness, and flame retardancy. ,Electricity Excellent in characteristics, suitable for power electronic parts, auto parts, frames, exterior parts, connectors. Further, since it has characteristics required for power electronic components, that is, glow wire characteristics, toughness, flame retardancy, and electrical characteristics, it is particularly suitable for connector parts.

The molded article obtained by molding the flame retardant polyamide resin composition of the present invention is particularly suitable for a liquid crystal television, a plasma display, a PDA, a small television, a radio, a notebook computer, a personal computer, a printer, and a whisk. Targets, PC peripherals, video recorders, DVD recorders, CD recorders, MD recorders, DAT recorders, amplifiers, cassette recorders, portable CD players, portable MD players, digital cameras Connectors for use in home phones, office phones, toys, medical equipment, electric cooker parts, microwave oven parts, audio parts, lighting parts, refrigerator parts, air conditioner parts, facsimile parts, and photocopier parts.

Example

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto. The measurement methods used in the examples and comparative examples are shown below.

(1) Resilience

According to ISO 1874-2, the injection molding machine NEX1000 manufactured by Nissei Resin Co., Ltd. was used, with a drum temperature of 300 ° C, a mold surface temperature of 100 ° C, a screw rotation number of 150 rpm, a parallel flow rate of 200 mm / sec, and injection/cooling = 20/20. Under the conditions of seconds, the pellets obtained in the examples and the comparative examples were injection molded to prepare test pieces of ISO Type-A specifications.

(a) tensile strain at break (when extremely dry)

The test piece obtained by the above method was vacuum-sealed in a moisture-proof bag of alumina. Using this test piece, the tensile strain at break was measured in accordance with the following standard method. When the tensile strain at break (at the time of extreme drying) is 3.0% or more, it is judged to be excellent in enthalpy.

Tensile strain: ISO 527-1, -2

(b) tensile fracture strain (when 3% water absorption)

The test piece obtained by the above method was immersed in warm water of 60 ° C, and the water absorption rate was determined from the change in the mass of the test piece. The tensile fracture strain was measured in the same manner according to the above standard method at a time when the water absorption rate was 3%. When the tensile strain at break (at 3% of water absorption) is 40% or more, it is judged that the enthalpy property at the time of water absorption is excellent.

(2) Flame retardancy

Using the pellets obtained in the examples and the comparative examples, the injection molding machine NEX1000 manufactured by Nissei Resin Co., Ltd. was used at a drum temperature of 280 ° C, a mold surface temperature of 80 ° C, a screw rotation number of 100 rpm, an injection pressure of 150 MPa, and an injection speed of 80 mm / Injection molding was carried out under the conditions of seconds, injection/cooling = 10/20 seconds, and a test piece of 127 mm × 12.7 mm × 1/64 inch was produced. The resulting test piece was used and evaluated for flame retardancy in accordance with UL94 specifications (specifications specified by Under Writer Laboratories Inc, USA).

(3) glow wire characteristics

The injection molding machine NEX1000 manufactured by Nissei Resin Co., Ltd. was used at a drum temperature of 280 ° C, a mold surface temperature of 80 ° C, a screw rotation number of 150 rpm, an injection pressure of 100 MPa, an injection speed of 100 mm/sec, and injection/cooling = 20/20 sec. The pellets obtained in the examples and the comparative examples were subjected to the conditions. Injection molding was carried out to prepare a test piece of 80 mm × 80 mm × corresponding thickness (mm). Further, the test piece was prepared in five types having thicknesses of 0.75 mm, 1.0 mm, 1.5 mm, 2.0 mm, and 3.0 mm. Using the obtained test piece, the glow wire ignition temperature (GW-IT) was measured in accordance with IEC60695-2-13. When all the test piece thicknesses were satisfied, it was set to pass when GW-IT: 825 ° C or more was satisfied.

(4) Anti-leakage

The injection molding machine NEX1000 manufactured by Nissei Resin Co., Ltd. was used at a drum temperature of 280 ° C, a mold surface temperature of 80 ° C, a screw rotation number of 150 rpm, an injection pressure of 100 MPa, an injection speed of 100 mm/sec, and injection/cooling = 20/20 sec. The pellets obtained in the examples and the comparative examples were injection-molded, and a test piece of 80 mm × 80 mm × 3 mm was produced. The resulting test piece was used in accordance with UL746A.

(5) Release property

The injection molding machine NEX1000 manufactured by Nissei Resin Co., Ltd. was used at a drum temperature of 280 ° C, a mold surface temperature of 80 ° C, a screw rotation number of 150 rpm, an injection pressure of 100 MPa, an injection speed of 100 mm/sec, and injection/cooling = 20/20 sec. The pellets obtained in the examples and the comparative examples were injection-molded to prepare a box-shaped molded article of 25 mm × 25 mm × 25 mm and a thickness of 1 mm. The load on the ejector plate when the film was released was measured with a load cell, and the value was taken as the release force. When the release force is less than 100N, it is set as acceptable.

Reference Example 1 Polyamine 6/polyamine 66 copolymerized resin (A2)

95.0 parts by mass of ε-caprolactam and 5.0 parts by mass of a salt of hexamethylenediamine and adipic acid are dissolved in pure water, and the amount of water is 1 part by mass as a raw material for polymerization, and the obtained The raw materials are sent to the polymerization tower. Profit The temperature of the polymerization tower is heated and adjusted by a heater installed in the upper portion, the middle portion, and the lower portion of the polymerization tower, and the raw material is reacted. The polymer discharged into the water bath was pelletized by a strand granulator, and the obtained pellet was subjected to hot water extraction at 95 ° C / 20 hours / bath ratio 20 times to remove unreacted raw materials and oligomers. . After the extraction, the mixture was dried under reduced pressure at 80 ° C / 30 hours to obtain a polyamine 6 /polyamine 66 copolymer resin (A2). The relative viscosity of 98% sulfuric acid according to JIS-K6810 was 2.75.

Reference Example 2 Polyamide 66/polyamine 6 copolymerized resin (A3)

3.0 parts by mass of ε-caprolactam and 97.0 parts by mass of a salt of hexamethylenediamine and adipic acid were put into a polymerization tank, and pure water was added so that the water became 45 parts by mass, and after replacing it with nitrogen gas in the polymerization tank , heat up to 260 ° C. Subsequently, the pressure was adjusted at 1.7 MPa for 1 hour, and after polymerization, the mixture was discharged and cut to obtain a polyamide-6/polyamine 6 copolymerized resin (A3). The relative viscosity of 98% sulfuric acid according to JIS-K6810 was 2.60.

Reference Example 3 Polyamide 66 resin (A4)

Polyamine 66 ("Amilan (registered trademark)" CM3001N manufactured by Toray Industries, Inc.: relative viscosity of 98% sulfuric acid 3.0) was used.

Reference example 4 Compound (B)

Made from Italmatch: MC25 (melamine cyanurate). Further, when the average particle diameter (number average value) was measured in accordance with JIS K5600-9-3, it was 4 μm.

Reference Example 5 Higher Fatty Acid Metal Salt (C1)

Made from Shengtian Chemical Co., Ltd.: Li-St (lithium stearate).

Reference Example 6 Carbamide amide wax (C2)

It is made of Kyoritsu Chemical Co., Ltd.: WH215 (polycondensate of ethylenediamine and sebacic acid, stearic acid).

[Examples 1 to 6]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 were used in the amounts shown in Table 1. The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) top-adding (post-loading) represented by Reference Example 6 to a 2-axis extruder ( Werner & Pfleiderer: ZSK57) was melt-kneaded under the conditions of a drum setting temperature of 290 ° C and a screw rotation number of 200 rpm, and was formed into a strand-shaped yarn, which was cooled in a cooling bath and then granulated by a cutter to obtain a pellet. Pellet. Using the obtained pellets, various characteristics were investigated in accordance with the aforementioned evaluation methods. Indicates the results in Table 1.

[Embodiment 7]

The polyamine 66 resin (A4) represented by Reference Example 3 and the three represented by Reference Example 4 The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 are the same as those in Example 1 in the amounts shown in Table 1. The mixture was melt-kneaded, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. Indicates the results in Table 1.

[Embodiment 8]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 are the same as those in Example 1 in the amounts shown in Table 1. The mixture was melt-kneaded, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. Indicates the results in Table 1.

[Embodiment 9]

Polyamine 66/polyamine 6 copolymerized resin (A3) represented by Reference Example 2, and three represented by Reference Example 4 The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 are the same as those in Example 1 in the amounts shown in Table 1. The mixture was melt-kneaded, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. Indicates the results in Table 1.

[Examples 10 to 13]

The polyamine 6/polyamine 66 copolymer resin (A2) represented by Reference Example 1, the polyamide 66/polyamine 6 copolymerized resin (A3) represented by Reference Example 2, and the reference example 4 are shown. Three The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 were mixed as shown in Table 2, and were the same as in Example 1. The mixture was melt-kneaded, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. The results are shown in Table 2.

[Embodiment 14]

The polyamine 6/polyamine 66 copolymer resin (A2) represented by Reference Example 1, the polyamide 66 resin (A4) represented by Reference Example 3, and the three represented by Reference Example 4 The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 were mixed as shown in Table 2, and were the same as in Example 1. The pellets were melt-kneaded to obtain pellets, and various characteristics were investigated in accordance with the aforementioned evaluation methods. The results are shown in Table 2.

[Comparative Example 1]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 The compound (B) was melt-kneaded in the same manner as in Example 1 in the amount shown in Table 3, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. The results are shown in Table 3.

[Comparative Example 2]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 The compound (B) and the higher fatty acid metal salt (C1) represented by Reference Example 5 were melt-kneaded in the same manner as in Example 1 in the same manner as in Example 1, and pellets were obtained in the same manner as in Example 1. The particles were investigated for various characteristics in accordance with the aforementioned evaluation methods. The results are shown in Table 3.

[Comparative Example 3~4]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 The compound (B) and the carboxylic acid amide amine wax (C2) shown in Reference Example 6 were melt-kneaded in the same manner as in Example 1 in the same manner as in Example 1, and were produced in the same manner as in Example 1. Pellets were obtained and the characteristics were investigated in accordance with the aforementioned evaluation methods. The results are shown in Table 3.

[Comparative Examples 5 to 10]

The polyamine 6/polyamine 66 copolymerized resin (A2) represented by Reference Example 1 and the three represented by Reference Example 4 The compound (B), the higher fatty acid metal salt (C1) represented by Reference Example 5, and the carboxylic acid amide amine wax (C2) represented by Reference Example 6 were mixed as shown in Table 3, and were the same as in Example 1. The mixture was melt-kneaded, and pellets were obtained in the same manner as in Example 1, and various characteristics were examined in accordance with the above-described evaluation method. The results are shown in Table 3.

Industrial utilization possibility

The flame retardant polyamide resin composition and the molded article of the present invention are excellent in moldability, and are excellent in glow wire properties, toughness, flame retardancy, and electrical properties, and are therefore suitable for use in power electronic parts, automobile parts, and frames. , exterior parts, connectors.

Claims (10)

A flame retardant polyamide resin composition comprising: polyamine resin (A), three Compound (B), and lubricant (C), the above polyamine resin (A), the aforementioned three The blending ratio of the compound (B) and the lubricant (C) is the above three with respect to 100 parts by mass of the polyamide resin (A). The compound (B) is 12 to 38 parts by mass, the lubricant (C) is 0.1 to 2.0 parts by mass, and the lubricant (C) contains (C1) / (C2) = 30/70 to 70/30 by mass ratio. Higher fatty acid metal salt (C1) and carboxylic acid amide amine wax (C2). The flame retardant polyamide resin composition according to claim 1, wherein the polyamine resin (A) is a hexamethyleneamine unit (a1) and a mass of at least 2% by mass to 98% by mass. Polyamide 6/polyamine 66 copolymerized resin (A1) of hexamethylene adipamide unit (a2) in an amount of 98% by mass or less. The flame retardant polyamide resin composition according to claim 2, wherein the polyamine resin (A) is a hexamethyleneamine unit (a1) and a mass of at least 50% by mass to 98% by mass. Polyamide 6/polyamine 66 copolymerized resin (A2) of hexamethylene adipamide unit (a2) of 50% by mass or more and 50% by mass or less. The flame retardant polyamide resin composition according to claim 3, wherein the polyamine resin (A) further comprises at least more than 50% by mass and 98% by mass or less of hexamethylenehexamethylenediamine. Amine unit 66 (polyamide 66) copolymerized resin (A3) having an amine unit (a2) and 2% by mass or more and less than 50% by mass of hexamethyleneamine unit (a1). A flame retardant polyamide resin composition according to claim 4, wherein the polyamine 6/polyamine 66 copolymerized resin (A2) and polyamine 66/polyamine 6 copolymerized resin (A3) The mass ratio is (A2) / (A3) = 15 / 85 ~ 85 / 15. The flame retardant polyamide resin composition according to claim 2, wherein the polyamine resin (A) further contains a polyamide 66 resin (A4). The flame retardant polyamide resin composition according to claim 3, wherein the polyamine resin (A) further comprises a polyfluorene 66 resin (A4). The flame retardant polyamide resin composition according to any one of claims 1 to 7, wherein the flame retardant polyamide resin composition is used for a drum temperature of 280 ° C and a mold surface temperature of 80 ° C. Each of the test pieces having a thickness of 0.75 mm, 1.5 mm, and 3 mm obtained by injection molding was subjected to a glow wire ignition temperature of 825 ° C or higher in accordance with the test of IEC 60695-2-13. A molded article obtained by molding, by injection molding, extrusion molding or blow molding, a flame retardant polyamide resin composition according to item 1 of the patent application. The molded article of claim 9, wherein the molded article is a frame, an exterior component or a connector.