JP2008189855A - Flame-retardant polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polyamide resin composition excellent in glow wire resistance, flame retardancy, and toughness in a thin-walled form and desirable for electrical and electronic parts such as connectors and to provide a molding comprising the same. <P>SOLUTION: The flame-retardant polyamide resin composition comprises from 100 pts.wt. of a polyamide resin (A) and 20-60 pts.wt. of a sulfate (B) of an aminotriazine compound. More desirably, the composition further contains 0.1-3 pts.wt., per 100 pts.wt. polyamide resin (A), of a dispersant (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant polyamide resin composition, and more particularly to a flame retardant polyamide resin composition excellent in glow wire property and toughness, which is one of the electrical safety characteristics of electrical / electronic equipment parts. is there.

  In general, polyamide resins are widely used for automotive electrical parts, electrical / electronic equipment parts, especially connectors and breakers because of their excellent moldability, mechanical properties, electrical properties, and chemical resistance. High performance and high performance have been realized according to the performance required for each part.

  However, in recent years, the required level for these parts, especially the required performance for electrical safety, has been increasing, and accordingly, higher functionality and higher performance are also expected for polyamide resins. . For example, for connectors, the required level of glow wire ignition temperature according to the IEC 60695-2-13 standard has been revised from 725 ° C. or higher to 775 ° C. or higher. For this reason, in the polyamide resin composition blended with melamine cyanurate, which has been conventionally used as a connector material, the glow wire ignition temperature required for the connector, for example, in a thick part such as a thickness of 3 mm is obtained. I found that I could not pass. On the other hand, miniaturization of parts has progressed, and there are cases where conventional connector materials have problems such as insufficient mechanical properties, particularly toughness, in thin portions (for example, hinge portions). That is, as a connector material, it is necessary to be excellent in both the glow wire property in the thick portion and the toughness in the thin portion.

  Patent Document 1 discloses a polyamide resin composition for a flame-retardant connector corresponding to the revision of the glow wire ignition temperature described above. In this patent document, in claim 1, “containing 100 parts by weight of a polyamide resin having a viscosity number of 85 to 140, 21 to 35 parts by weight of a triazine flame retardant, and 0.01 to 0.3 part by weight of a carboxylic acid amide wax. Although a flame retardant polyamide resin composition characterized by comprising `` is shown, there is no description of sulfate as a triazine flame retardant, and a thin molded product formed by molding the resin composition is: There was a problem that the tensile elongation was low and fragile.

  On the other hand, Patent Document 2 discloses a flame retardant resin composition comprising 100 parts by weight of a thermoplastic resin and 10 to 300 parts by weight of a triazine compound sulfate such as melamine sulfate and benzoguanamine sulfate. However, regarding thermoplastic resins, it is described that “especially polyolefins are preferably used”, there is no description of examples using polyamide resins, and there is no description of glow wire properties. Moreover, the thermoplastic resin composition described in the patent document has a problem that the flame retardance of the thin portion is low.

  Patent Documents 3 to 5 relate to a resin composition in which a melamine-based flame retardant and other components are blended in a thermoplastic resin, but in this document, a resin composition in which melamine sulfate is blended in a polyamide resin in the examples is illustrated. There is no description about tensile elongation and glow wire property. Further, as in the examples of Patent Document 3, when a polyester resin is used, the toughness is inferior, and as described in Patent Document 4, melamine polyphosphate, melam, melem double salt, melamine polymetaphosphate, polyphosphate amide, etc. When the flame retardant is used, there is a problem that the glow wire property is low. Furthermore, in the thermoplastic resin composition as described in the examples of Patent Document 5, the glow wire property and the thin toughness may be low.

  Patent Document 6 discloses a flameproof artificial turf yarn comprising 99.9 to 97.0 parts by weight of a polyamide resin and 0.1 to 3.0 parts by weight of a melamine flame retardant. Describes a resin composition comprising 98.0% by weight of nylon 6 and 2.0% by weight of melamine sulfate. Patent Document 7 contains at least one selected from the group of melamine compounds having an average particle size of more than 10 microns and 100 microns or less as a flame retardant in a powder coating mainly composed of polyamide. A composition for a polyamide-based flame-retardant powder coating is shown. In Example 2, a composition in which 5% by weight of melamine sulfate is blended with a powder coating made of polyamide 11 is described. However, the resin compositions described in these patent documents have different uses, and furthermore, since the blending amount of melamine sulfate is small, the flame retardancy and glow wire property required for electric / electronic device parts cannot be achieved. Moreover, there is no description regarding the tensile elongation of the molded product.

  In Patent Document 8, ammonium polyphosphate (C) is used in an amount of 10 to 40 wt% with respect to 100 parts by weight of a composition comprising 95 to 10 wt% of a rubber-reinforced styrene resin (A) and 5 to 90 wt% of a polyamide resin (B). The flame-retardant thermoplastic resin composition characterized by mix | blending 0.5 part by weight and 0.5 to 10 weight part of melamine sulfate and / or ammonium sulfate (D) is shown. However, in this patent document, it is essential to use a polyamide resin and a rubber-reinforced styrene-based resin in combination as a resin component. In such a resin composition, the glow wire property may be lowered. Moreover, there is no description regarding the tensile elongation.

  Patent Document 9 discloses a flame retardant reinforced polyamide resin composition comprising (a) a polyamide resin, (b) a compound having a triazine ring having a weight reduction temperature of 400 ° C. or higher, and (c) an inorganic reinforcing material, When the weight percentages of the components (a), (b) and (c) in the product are A, B and C wt%, respectively, 1 ≦ B / A ≦ 2, 5 ≦ C ≦ 50, A + B + C = 100 A flame retardant reinforced polyamide resin composition characterized by having a blending ratio satisfying the formula is shown, and melamine sulfate is mentioned as an example of the component (b). However, since the resin composition has a large amount of component (b), mechanical properties such as tensile elongation are lowered. In addition, the patent document does not describe the glow wire property.

JP-A-2005-171232 JP-A-8-48812 JP-A-11-343389 JP 2003-226818 A WO2003 / 046084 JP 2000-303257 A JP 2002-161235 A JP 2000-44763 A JP 2000-119512 A

  Under such circumstances, an object of the present invention is to provide a flame retardant polyamide resin composition excellent in flame retardancy, glow wire property and toughness, and more specifically, flame retardancy of a molded product having a thickness of 0.8 mm according to UL94 standard. Is a polyamide resin composition having a glow wire ignition temperature of 775 ° C. or higher for a molded product having a thickness of 3 mm or less according to IEC 60695-2-13 standard, and a molded product comprising the same. It is in.

  As a result of diligent studies to solve the above-mentioned problems, it was found that by blending a specific amount of a sulfate of an aminotriazine compound with a polyamide resin, the desired flame retardancy, glow wire property and thin toughness can be satisfied at the same time. Has been completed.

  The subject matter of the first aspect of the present invention is a flame retardant polyamide resin comprising 20 to 60 parts by weight of an aminotriazine compound sulfate (B) in 100 parts by weight of a polyamide resin (A). Present in the composition.

The gist of the second invention of the present invention resides in a molded product obtained by molding the flame retardant polyamide resin composition described in the first invention.

The flame-retardant polyamide resin composition and molded article of the present invention have the following particularly advantageous effects, and their industrial utility value is extremely high.
1. The flame retardant polyamide resin composition of the present invention is excellent in flame retardancy and glow wire properties. In particular, the flame retardancy of a molded product having a thickness of 0.8 mm according to the UL94 standard is V-0, and the glow wire ignition temperature of a molded product having a thickness of 3 mm or less according to the IEC60695-2-13 standard is 775 ° C. or higher.
2. The flame-retardant polyamide resin composition of the present invention has excellent tensile elongation even in a thin portion (for example, a thickness of 1 mm or less).
3. Since the molded product formed by molding the flame-retardant polyamide resin composition of the present invention is excellent in toughness and electrical safety, as a component or instrument for connecting wiring between electrical devices such as connectors or inside the device. Useful.

Hereinafter, the present invention will be described in detail.
Polyamide resin (A)
The polyamide resin (A) in the present invention is a polyamide resin obtained by polycondensation using a polymerizable ω-amino acid, a lactam, preferably a lactam having a three or more ring, a dicarboxylic acid, and a diamine as raw materials, or These polyamide copolymers and blends.

Examples of ω-amino acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 2-chloro-paraaminomethylbenzoic acid, 2-methyl- Examples include aromatic amino acids such as paraaminomethylbenzoic acid and 4-aminomethylbenzoic acid.
Examples of the lactam include ε-caprolactam, enantolactam, capryl lactam, lauryl lactam, α-pyrrolidone, α-piperidone and the like.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acid and aromatic dicarboxylic acid.
Specific examples of the aliphatic dicarboxylic acid include, for example, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadioic acid, hexadecadioic acid, hexadecenedioic acid, eicosandioic acid Eicosadienedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid and the like. The aliphatic dicarboxylic acid includes alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
The aromatic dicarboxylic acid is a dicarboxylic acid having at least one aromatic ring such as a benzene ring or a naphthalene ring in the molecule. Specific examples thereof include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, Examples include 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and xylylene dicarboxylic acid.

Examples of diamines include aliphatic diamines and aromatic diamines.
Specific examples of the aliphatic diamine include, for example, pentamethylene diamine, hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4 (or 2,4,4)- And trimethylhexamethylenediamine. In addition, bis- (4,4′-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, Aliphatic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and 2,2-bis (4-aminocyclohexyl) propane are also included in the aliphatic diamine.
The aromatic diamine is a diamine having at least one aromatic ring such as a benzene ring or a naphthalene ring in the molecule, and specific examples thereof include metaxylylenediamine and paraxylylenediamine.

  As a raw material for the polyamide resin as described above, a compound having 5 to 10 carbon atoms is preferable. By setting the number of carbon atoms to 5 or more, the thin wall toughness can be made more excellent, and by setting the number of carbons to 10 or less, the flame retardancy can be made more preferable. More specifically, ε-caprolactam as a lactam, adipic acid as an aliphatic dicarboxylic acid, terephthalic acid or isophthalic acid as an aromatic dicarboxylic acid, pentamethylenediamine, hexamethylenediamine, or aromatic diamine as an aliphatic diamine Xylylenediamine is more preferable because it is readily available and advantageous in terms of price.

  A salt composed of diamine and dicarboxylic acid can be obtained by neutralization in an aqueous solution under pressure and high temperature. The salt thus obtained, the above-mentioned ω-amino acid and lactam are subjected to an oligomerization reaction by condensing under high pressure and high temperature, and then polymerized to an appropriate melt viscosity by reducing the pressure. It can be advanced to produce the polyamide resin used in the present invention.

The polyamide resin (A) in the present invention is preferably an aliphatic polyamide resin and a semi-aromatic polyamide resin as shown below.
Examples of the aliphatic polyamide resin include polyamide 6 mainly composed of ε-caprolactam or ε-aminocaproic acid, polyamide 56 mainly composed of a salt of pentamethylenediamine and adipic acid, and salt of hexamethylenediamine and adipic acid. Examples include polyamide 66 as a raw material, polyamide 6/66 copolymer mainly composed of a salt of hexamethylenediamine and adipic acid and ε-caprolactam or ε-aminocaproic acid. These polyamide resins are blended in two or more types. May be used.
The aliphatic polyamide resin preferably has a viscosity number of 70 to 200 ml / g measured at a temperature of 25 ° C. and 96 wt% sulfuric acid at a polyamide resin concentration of 0.5 wt% in accordance with ISO307. By making the viscosity number 70 ml / g or more, the toughness and the appearance of the molded product can be made excellent. By making the viscosity number 200 ml / g or less, the compound property and the molding processability become easy, and the good glow wire property. And it is preferable because it can have a molded product appearance.

  The semi-aromatic polyamide resin is a polyamide resin comprising at least one polyamide constituent unit (a) selected from a salt comprising an aliphatic diamine and an aromatic dicarboxylic acid, a salt comprising an aromatic diamine and an aliphatic dicarboxylic acid, or A polyamide copolymer comprising these polyamide constituent units (a) and at least one aliphatic polyamide constituent unit (b) selected from a salt comprising lactam or aliphatic diamine and aliphatic dicarboxylic acid, Has a weight ratio of units (a) and (b) of (a) / (b) = 100/0 to 5/95. A more preferred weight ratio is (a) / (b) = 100/0 to 7.5 / 92.5. From the viewpoint of mechanical properties such as crystallization speed and rigidity, (a) / (b) = The range of 100/0 to 30/70 is more preferable. By setting it as such a polyamide structural unit, glow wire property and a flame retardance can be improved more. Specific examples of such a preferred semi-aromatic polyamide resin include, for example, polyamide MXD6 mainly composed of a salt of metaxylylenediamine and adipic acid, metaxylylenediamine, paraxylylenediamine and adipic acid as the main raw materials. Polyamide MP6, polyamide 6I mainly composed of a salt of hexamethylenediamine and isophthalic acid, a salt of hexamethylenediamine and adipic acid / a copolymer of a salt of hexamethylenediamine and isophthalic acid (polyamide 66 / 6I), Examples include a salt of hexamethylenediamine and isophthalic acid / a copolymer of hexamethylenediamine and terephthalic acid (polyamide 6I / 6T), and more preferably polyamide MXD6, polyamide MP6, and polyamide 6I / 6T. .

The semi-aromatic polyamide resin preferably has a specific melt viscosity. A preferable melt viscosity is 750 to 8000 poise, more preferably 800 to 7000 poise, measured using a capillary rheometer (Capillograph 1C manufactured by Toyo Seiki Co., Ltd.) at a temperature of 280 ° C. and a shear rate of 100 sec ⁻¹ . More preferably, it is 850 to 6000 poise. By setting the melt viscosity to 750 poise or more, the glow wire property and mechanical strength tend to be excellent, and by setting the melt viscosity to 8000 poise or less, flame retardancy is kept good and flowability and moldability are prevented from being lowered. Is preferable.

  In addition, since the aminotriazine compound sulfate described later begins to decompose when the temperature at the time of melting the resin composition reaches 290 ° C. or higher, in order to suppress the occurrence of molding defects and ensure glow wire properties and flame retardancy The resin composition is preferably produced and molded under the condition that the resin temperature is 290 ° C. or lower. However, at a low temperature of 290 ° C. or lower, the dispersibility of the sulfate of the aminotriazine compound at the time of producing the resin composition may be lowered, or the fluidity at the time of molding the resin composition may be lowered, and thin wall molding may be difficult. Therefore, as the polyamide resin of the present invention, it is preferable to use a polyamide resin having a melting point as low as possible below 290 ° C. and capable of ensuring glow wire properties and flame retardancy.

  The terminal of the polyamide resin (A) in the present invention may be sealed with a carboxylic acid or an amine, and when sealing the terminal, it is preferable to seal with a carboxylic acid having 6 to 22 carbon atoms or an amine. . Specifically, examples of the carboxylic acid used for sealing include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine. The amount of carboxylic acid or amine used for sealing is preferably about 30 μeq / g from the viewpoint of melt viscosity at the time of molding the resin composition.

Sulfate of aminotriazine compound (B)
The aminotriazine compound can be represented by the following general formula (1). The most common triazine is 1,3,5-triazine. The hydrocarbon group substituted with triazine is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group or a propyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group. Up to three amino groups can be substituted, and any of these compounds can be used in the present invention.
The sulfate of an aminotriazine compound used in the present invention is a sulfate of an aminotriazine compound in which at least one amino group is substituted on a triazine or a substituted triazine substituted with a hydrocarbon group or the like.

但し、Ｒ₁及びＲ_２は、アミノ基、炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基である。

However, R < ₁ > and R < ₂ > is an amino group, a C1-C4 alkyl group, or a C6-C10 aryl group.

  Specific examples of the aminotriazine compound include melamine, benzoguanamine, methylguanamine and the like, and two or more kinds can be used in combination.

  The particle size of these aminotriazine compounds is not particularly limited, but from the viewpoint of mechanical strength and appearance of the molded product, those having an average particle size (median diameter) of 0.1 to 50 μm are preferable, and those of 0.1 to 30 μm are preferable. More preferred.

  Further, sulfuric acid can be used without particular limitation as long as it is generally available. The concentration of sulfuric acid is not particularly limited, and either concentrated sulfuric acid or dilute sulfuric acid can be used, but dilute sulfuric acid is preferably used from the viewpoint of handling.

  There is no restriction | limiting in particular as a manufacturing method of the sulfate of an aminotriazine compound, A conventionally well-known method is mentioned. For example, a method in which sulfuric acid is added little by little at room temperature in a state where the aminotriazine compound is dispersed in water in advance, a method in which the aminotriazine compound is pulverized with a ball mill or the like at room temperature, and sulfuric acid is added with stirring. Aminotriazine in sulfuric acid Examples include a method of adding a compound.

  The proportion of sulfur atoms in the sulfate of the aminotriazine compound is preferably 3 to 20% by weight because there is little phenomenon of contaminating substances adhering to the mold during molding. In addition, let this sulfur atom amount be the total amount of what has formed the amino triazine compound and the salt, and the free thing which has not formed.

  As the sulfate of the aminotriazine compound of the present invention, melamine sulfate is preferred. Melamine sulfate can be produced, for example, using the method described in JP-A-8-231517.

  The compounding quantity of the sulfate (B) of an aminotriazine compound is 20-60 weight part with respect to 100 weight part of polyamide (A), Preferably it is 25-50 weight part. Glow wire properties can be effectively improved by setting the blending amount to 20 parts by weight or more, and setting to 60 parts by weight or less is preferable because the toughness can be kept good.

Dispersant (C)
In the flame-retardant polyamide resin composition of the present invention, since the sulfate of the aminotriazine compound is blended at a high concentration, aggregation of the sulfate is prevented and dispersibility is further improved. In order to suppress a decrease in mechanical strength, it is preferable to add a dispersant (C). However, since the dispersant may reduce the flame retardancy and glow wire property of the resin composition, it is necessary to carefully select the type and blending amount thereof. In the present invention, at least one selected from the group consisting of carboxylic acid amide waxes, higher fatty acid metal salts and higher fatty acid ester compounds can be suitably used. Of these, the carboxylic acid amide waxes have the effect of improving the releasability when injection molding of electrical and electronic equipment parts such as connectors without reducing the flame retardancy of the resin composition and the ignition temperature of the glow wire. It is particularly preferable because it is large and can improve moldability. The above three types of dispersants have the effect of improving the dispersibility of the sulfate of the aminotriazine compound, and also the effect of improving the releasability during molding.

Examples of the carboxylic acid amide wax include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.
The higher aliphatic monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid or hydroxycarboxylic acid having 16 or more carbon atoms, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. .
The polybasic acid is a dibasic acid or higher carboxylic acid, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, azelaic acid, and phthalic acid, terephthalic acid, etc. Aromatic dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid and cyclohexyl succinic acid can be mentioned.
Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

  As the carboxylic acid amide wax, a compound obtained by polycondensation of stearic acid, sebacic acid and ethylenediamine is preferable, and a compound obtained by reacting 2 mol of stearic acid, 1 mol of sebacic acid and 2 mol of ethylenediamine and polycondensation is more preferable. .

The higher fatty acid metal salt includes, for example, metal salts of the above-mentioned higher aliphatic monocarboxylic acids, and specifically, calcium stearate, barium stearate, magnesium stearate, aluminum stearate, zinc stearate, and montanic acid. Calcium and the like are preferable.
Examples of the higher fatty acid ester compound include ester compounds of the above-mentioned higher aliphatic monocarboxylic acids and alcohols. Specifically, stearyl stearate, glycerin stearate, pentaerythritol stearate and the like are preferable.

  The blending amount of the dispersant (C) is preferably 0.01 to 3 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the polyamide resin (A). By setting the blending amount to 0.01 parts by weight or more, it is possible to further disperse the sulfate of the aminotriazine compound and prevent a decrease in toughness, and to improve the releasability at the time of molding. Further, it is preferable that the blending amount is 3 parts by weight or less because it is possible to prevent a decrease in mechanical strength and flame retardancy and to prevent problems such as plate-out and blooming.

  In the present invention, pigments, dyes, fillers, nucleating agents, foaming agents, mold release agents, thermal stabilizers, light stabilizers, antistatic agents, rust preventives, aminotriazines, as long as the object of the present invention is not impaired. A flame retardant other than the sulfate of the compound and other conventionally known resin additives can be blended.

  As a method of blending the sulfate (B) of the aminotriazine compound with the polyamide resin (A), various conventionally known methods can be used at any stage up to immediately before molding the desired molded product. Can do. For example, (1) each component is weighed at a predetermined ratio and mixed with a blender to obtain a dry blend, (2) the dry blend obtained in (1) above is melt-kneaded with a single-screw or twin-screw extruder. , A method of pelletizing, (3) a method of preparing a master pellet in which a sulfate of an aminotriazine compound larger than a predetermined amount is previously kneaded in a polyamide resin, and dry blending this with the remaining polyamide resin for dilution, etc. It is done. When melt-kneading, it is preferable that the resin temperature does not exceed 290 ° C. By setting it as 290 degrees C or less, it can suppress that a glow wire ignition temperature falls because the sulfate of an amino triazine compound decomposes | disassembles.

  In producing a molded article such as an electric / electronic device part using the polyamide resin composition of the present invention, the dry blended product or the pellet-shaped polyamide resin composition of the above (1) to (3) are conventionally used. Known molding methods such as injection molding, extrusion molding and the like can be used. Among these, it is preferable to use an injection molding method from the viewpoint of productivity and product performance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to the example described below, unless the summary is exceeded. In addition, the detail of each component used in the Example described below is as follows. Moreover, evaluation about the polyamide resin composition comprised from these components was performed by the method as described below.

[Ingredients used in Examples]
Polyamide resin (A-1) Polyamide 6: “Product name: Novamid (registered trademark) 1013J” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity 138 ml / g, melting point 224 ° C.
(A-2) Polyamide 6/66 copolymer: “Novamid (registered trademark) 2010J” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity number 118 ml / g, melting point 198 ° C.
(A-3) Polyamide 6I / 6T copolymer: “Novamid (registered trademark) X21” manufactured by Mitsubishi Engineering Plastics Co., Ltd., salt of hexamethylenediamine and isophthalic acid / hexamethylenediamine and terephthalic acid Copolymer
Flame retardant (B-1) Melamine sulfate: “Product name: Apinone 901” manufactured by Sanwa Chemical Co., Ltd. 9% by weight of sulfur component in melamine sulfate, average particle size (catalog value) 17 ± 2.0 μm
(B-2) Melamine cyanurate: pulverized “trade name: MX44” manufactured by Mitsubishi Chemical Corporation. Average particle diameter (median diameter) 2μm
(B-3) Melamine polyphosphate: “trade name: PMP 200” manufactured by Nissan Chemical Industries, Ltd., average particle diameter (median diameter) 2.5 μm
Dispersant (C-1) Carboxylic acid amide wax: “Product name: WH255” manufactured by Kyoeisha Chemical Co., Ltd., polycondensate of stearic acid, sebacic acid and ethylenediamine (C-2) Calcium stearate: “Product” manufactured by Sakai Chemical Industry Co., Ltd. Name: SC-100 "

[Evaluation methods]
(1) Glow wire properties: Measured on test pieces having a size of 80 mm × 80 mm and thicknesses of 1 mm, 2 mm, and 3 mm in accordance with IEC60695-2-13 standard. Tests were performed at intervals of 25 ° C. and evaluated at the highest temperature at which no ignition occurred. It can be judged that the higher the ignition temperature, the better the glow wire property.
(2) Flame retardancy: Measured on a test piece having a size of 127 mm × 12.7 mm and a thickness of 0.8 mm in accordance with the UL94 standard. As for the flame retardancy by this test, V-0 is good and V-2 is inferior to V-0.
(3) Tensile elongation: A JIS No. 4 dumbbell piece having a thickness of 1 mm was molded, and the tensile elongation was measured in accordance with JIS K7113 standard. Since the elongation at the yield point was 2.5%, it can be judged that the higher the value exceeds 2.5%, the better the toughness.

[Examples 1-8, Comparative Examples 1-8]
Preparation of Polyamide Resin Composition and Test Specimen Preparation Method Polyamide resin, flame retardant and various additive components were weighed in the blending amounts shown in Tables 1 and 2 and mixed with a tumbler mixer for 30 minutes to obtain a mixture. The obtained mixture was melt-kneaded with a twin screw extruder (manufactured by Nippon Steel Works, model: TEX30HCT, screw diameter 30 mm) under the conditions of a cylinder temperature of 260 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 15 kg / h. Polyamide resin composition pellets were obtained.
The obtained polyamide resin composition was vacuum-dried at 120 ° C. for 8 hours, and then injection-molded at a resin temperature of 265 ° C. and a mold temperature of 80 ° C. using an injection molding machine (manufactured by Nippon Steel Works, J75ED). The above test pieces were prepared. Using the obtained test piece, the glow wire property, flame retardancy, and tensile elongation were evaluated. The evaluation results are shown in Tables 1 and 2.

From Table 1, the following became clear.
1. From the comparison of Examples 1 to 8 and Comparative Examples 1 to 8, by adding melamine sulfate as a flame retardant, the flame resistance can improve the glow wire property and the tensile elongation while maintaining V-0. did it.
2. From the comparison between Example 2 and Comparative Example 3, when the melamine sulfate is less than the range of the present invention, the glow wire property and flame retardancy cannot achieve the object of the present invention.
3. From the comparison of Examples 5 and 6 and Comparative Example 7, when the melamine sulfate exceeds the range of the present invention, the tensile elongation is lower than the yield point elongation and there is a problem in toughness.

  As described in detail above, the flame-retardant polyamide resin composition of the present invention has excellent glow wire properties and excellent flame retardancy and thin-wall toughness. It is suitable for a connector material widely used as a component such as a home appliance, a communication device, an OA device, a computer, or a car electronics device. Further, the connector formed by molding the flame retardant polyamide resin composition of the present invention has a structure in which, for example, a plurality of electric wires and cables can be inserted, and such electric wires and cables are inserted. The connector is used when fitting the fitting portion and connecting the wiring.

Claims (6)

A flame retardant polyamide resin composition comprising 20 to 60 parts by weight of an aminotriazine compound sulfate (B) in 100 parts by weight of a polyamide resin (A). The flame-retardant polyamide resin composition according to claim 1, wherein the sulfate (B) of the aminotriazine compound is melamine sulfate. Further, at least one dispersant (C) selected from the group consisting of a carboxylic acid amide wax, a higher fatty acid metal salt, and a higher fatty acid ester is added in an amount of 0.1 to 3 with respect to 100 parts by weight of the polyamide resin (A). The flame retardant polyamide resin composition according to claim 1 or 2, wherein the flame retardant polyamide resin composition is blended in parts by weight. The molded article formed by shape | molding the flame-retardant polyamide resin composition of any one of Claims 1-3. The molded article according to claim 4, which is an electric / electronic device part. The molded article according to claim 5, which is a connector.