JP2007231094A - Flame-retardant reinforced polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin molded article having excellent flame retardancy even if an inorganic filler such as a glass fiber is contained, not generating a halogen-based gas or the like at burning, and having excellent mechanical properties and electric characteristics; and to provide a flame-retardant reinforced polyamide resin composition constituting the molded article. <P>SOLUTION: The flame-retardant reinforced polyamide resin composition contains (A) a polyamide resin, (B) an inorganic filler and (C) a flame retardant. The flame retardant contains (c1) a phosphinic acid salt-based compound and (c2) a reaction product of phosphoric acid with melamine and/or a reaction product of cyanuric acid with the melamine, regulated so that the ratio (c1/c2) of the contents thereof may be 2-25, and the total content thereof may be 10-30 wt.% based on the whole amount of the composition. The molded article comprises the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant reinforced polyamide resin composition.

  Polyamide resins are excellent in mechanical properties and heat resistance, and thus are widely used in fields such as electric / electronics, automobiles, machinery, and building materials. In particular, electrical components such as connectors are required to have a high level of flame retardancy, and generally a method of adding a halogen flame retardant or a triazine flame retardant is employed. For example, addition of brominated flame retardants to polyamide resin, for example, decabromodiphenyl ether (Patent Document 1), addition of brominated polystyrene (Patent Documents 2 and 3), addition of brominated polyphenylene ether (Patent Document 4), bromine Addition of a modified styrene-maleic anhydride polymer (Patent Document 5) and the like are known. In particular, polyamide resin compositions containing these halogen-based flame retardants and reinforcing materials (glass fibers and the like) have been widely used for connectors because of their excellent flame retardancy and mechanical properties.

  However, halogen flame retardants are said to have adverse effects on the environment and the human body, such as corrosive halogen gases and harmful substances generated during combustion, and there is a movement to regulate the use of halogen flame retardants. For this reason, halogen-free triazine flame retardants have attracted attention and many studies have been made. For example, a technique using melamine as a flame retardant (Patent Document 6), a technique using cyanuric acid (Patent Document 7), and a technique using melamine cyanurate (Patent Document 8) are well known. These technologies can achieve flame retardance conforming to the UL94 V-0 standard with a thickness of 1/32 inch in a system that does not contain a reinforcing material, but when reinforced with glass fiber, a large amount of flame retardant is blended. Even if this occurs, there is a problem in that cotton ignition occurs and it does not conform to the UL94 V-0 standard. Note that the V94 standard of the UL94 standard is an evaluation rank that is recognized as being most difficult to ignite and having excellent flame retardancy in a standard defined by Under Writers Laboratories Inc. of the United States.

On the other hand, flame retardant technology (Patent Document 9) using melamine phosphate, melamine pyrophosphate, or melamine polyphosphate, which is an intumescent flame retardant, in a glass fiber reinforced polyamide resin has been proposed. In order to satisfy the UL94 V-0 standard with an inch thickness, it is necessary to add a lot of these melamine phosphate flame retardants, so electrical properties such as toughness, mechanical properties and tracking resistance In some cases, the characteristics deteriorated, and it could not be said to be satisfactory in practical use.
JP 47-7134 A JP 51-47044 A JP-A-4-175371 JP 54-1116054 A Japanese Patent Laid-Open No. 3-168246 Japanese Examined Patent Publication No. 47-1714 JP 50-105744 A JP-A-53-31759 Japanese National Patent Publication No. 10-505875

  The present invention has excellent flame retardancy even when an inorganic filler such as glass fiber is contained, does not generate halogen gas during combustion, and has excellent mechanical properties and electrical properties. An object of the present invention is to provide a product and a flame-retardant reinforced polyamide resin composition constituting the molded product.

  The present invention comprises (A) a polyamide resin, (B) an inorganic filler, and (C) a flame retardant, wherein the flame retardant is (c1) a phosphinate compound and (c2) phosphoric acid and melamine Reaction products and / or reaction products of cyanuric acid and melamine, the content ratio thereof is 2 to 25 by mass ratio (c1 / c2), and the total content thereof is based on the total amount of the composition The present invention relates to a flame retardant reinforced polyamide resin composition characterized by being 10 to 30% by weight, and a molded article comprising the composition.

  The polyamide resin composition of the present invention and a molded product comprising the composition are extremely flame retardant even when an inorganic filler such as glass fiber is contained, and does not generate highly corrosive hydrogen halide gas during combustion. . In addition, it has excellent mechanical properties such as tensile strength, tensile elongation, bending strength, flexural modulus impact resistance, and toughness, and electrical characteristics.

  The flame retardant reinforced polyamide resin composition of the present invention comprises (A) a polyamide resin, (B) an inorganic filler, and (C) a flame retardant.

(A) polyamide resin;
The polyamide resin is a polymer having an amide bond in the main chain, the main raw material of which is aminocarboxylic acid, lactam or diamine and dicarboxylic acid (including a pair of salts thereof). Preferable specific examples of the polyamide resin include, for example, polycapramide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycoupleramide / polyhexamethylene adipamide copolymer (nylon) 6/66), polyundecamide (nylon 11), polycapramide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycoupler / polydodecanamide copolymer (nylon 6/12), polyhexamethylene sebacamide (Nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalia (Nylon 6T), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polycapramide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polycoupleramide / polyhexamethylene isophthalamide copolymer (nylon) 6 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polytrimethylhexamethylene terephthalate Amide (nylon TMDT), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocycle) Hexyl) methane dodecamide (nylon dimethyl PACM12), poly-m-xylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T) and mixtures thereof. Of these, nylon 6, nylon 66, or a mixture thereof is particularly preferable.

  The relative viscosity of the polyamide resin is preferably in the range of 1.7 to 2.7, and more preferably in the range of 1.9 to 2.6, from the viewpoint of further improving the flame retardancy and mechanical properties of the molded product. More preferably. When using 2 or more types of polyamide resins, the relative viscosity of those mixed resins should just be in the said range.

  The content of the polyamide resin is usually 30 to 85% by mass, preferably 40 to 80% by mass, based on the total amount of the composition, from the viewpoint of further improving the flame retardancy, mechanical properties and moldability of the molded product. %.

(B) inorganic filler;
Any inorganic filler that has been conventionally contained as an inorganic reinforcing material in the field of polyamide resin molded products can be used. Specific examples include, for example, glass fiber, carbon fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, basalt fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as wollastonite, glass beads, glass flakes, and titanium oxide. Two or more of these reinforcing materials may be used in combination. In particular, glass fiber, wollastonite, talc, calcined kaolin and mica are preferably used. The glass fiber can be selected from long fiber type roving, short fiber type chopped strand, milled fiber, and the like. It is preferable to use a glass fiber that has been surface-treated for polyamide.

  The content of the inorganic filler is usually 5 to 40% by mass based on the total amount of the composition from the viewpoint of further improving the mechanical properties of the molded product and improving the melt-kneading processability of the composition. The amount is preferably 10 to 35% by mass.

(C) flame retardant;
In the present invention, the flame retardant is (c1) a phosphinate compound (sometimes referred to herein as a flame retardant (c1)); and (c2) a reaction product of phosphoric acid and melamine and / or cyanuric acid; Reaction product with melamine (sometimes referred to herein as flame retardant (c2));
Is used. By using such a flame retardant (c1) and a flame retardant (c2) in combination, excellent flame retardancy can be exhibited even when the inorganic filler is contained. Moreover, since the flame retardant (c1) and the flame retardant (c2) do not contain a halogen atom, no halogen gas or the like is generated during combustion. Furthermore, since the contents of the flame retardant (c1) and the flame retardant (c2) are relatively small, excellent mechanical properties and electrical characteristics can be ensured. If one of the flame retardant (c1) or the flame retardant (c2) is not contained, sufficient flame retardancy cannot be obtained.

  The flame retardant (c1) is a phosphinate compound, and more specifically, a phosphinate represented by the following formula (I), a diphosphinate represented by the following formula (II), or a mixture thereof.

In formulas (I) and (II), R ¹ , R ² , R ⁴ and R ⁵ are each independently a linear or branched C _{1 to} C ₁₆ alkyl group or an aryl group, and R ¹ and R ² and R ⁴ and R ⁵ may form a ring with each other. Preferred alkyl groups are C ₁ -C ₈ alkyl groups, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-octyl. A preferred aryl group is a phenyl group. More preferably R ¹ and R ² are each independently a linear C ₁ -C ₃ alkyl group (eg, a methyl group, an ethyl group, or an n-propyl group) or an aryl group (eg, a phenyl group), and more preferably Each independently represents a linear C ₁ -C ₃ alkyl group, particularly an ethyl group. More preferably R ⁴ and R ⁵ are each independently a linear C ₁ -C ₃ alkyl group (eg, a methyl group, an ethyl group, or an n-propyl group) or an aryl group (eg, a phenyl group), and more preferably Each independently represents a linear C ₁ -C ₃ alkyl group, particularly a methyl group.

R ³ is a linear or branched C _{1 to} C ₁₀ alkylene group, an arylene group, an alkylarylene group, or an arylalkylene group.
The alkylene group is a divalent saturated aliphatic hydrocarbon group. Preferred examples include methylene group, ethylene group, trimethylene group, propylene group, propylidene group, tetramethylene group, 1,1-dimethylethylene group, pentane. A methylene group, an octamethylene group, a dodecamethylene group, etc. are mentioned.
The arylene group is a divalent aromatic hydrocarbon group, and preferred specific examples include a phenylene group and a naphthylene group.
The alkylarylene group is a divalent aromatic hydrocarbon group in which 1 to 3, preferably 1 C _{1 to} C ₄ alkyl groups are substituted. Preferred specific examples include, for example, methylphenylene group, ethylphenylene Group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, tert-butylnaphthylene group and the like.
The arylalkylene group is a divalent C ₁ -C ₄ saturated aliphatic hydrocarbon group in which 1 to 3, preferably 1 aryl group is substituted. Preferred specific examples include, for example, phenylmethylene group, phenyl An ethylene group, a phenylpropylene group, and a phenylbutylene group.
More preferred R ³ is a C ₁ -C ₃ alkylene group, an arylene group, an alkylarylene group, particularly a methylene group, an ethylene group, a phenylene group, a methylphenylene group, or an ethylphenylene group.

M is a calcium, magnesium, aluminum, or zinc atom in common with the formulas (I) and (II), preferably an aluminum or zinc atom, particularly an aluminum atom.
m is 2 or 3 in common with the formula (I) and the formula (II).
n is 1 or 3.
x is 1 or 2.
However, in the formula (II), mx = 2n.

  Preferable specific examples of the phosphinic acid that can constitute the phosphinic acid salt represented by the above formula (I) include, for example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid and the like. .

  Preferred specific examples of the phosphinic acid salt represented by the above formula (I) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphinic acid. Magnesium, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, methyl-n-propylphosphinic acid Examples include magnesium, aluminum methyl-n-propylphosphinate, and zinc methyl-n-propylphosphinate.

  Preferable specific examples of diphosphinic acid that can constitute the diphosphinic acid salt represented by the above formula (II) include, for example, methandi (methylphosphinic acid), benzene-1,4-di (methylphosphinic acid) and the like.

Preferable specific examples of the diphosphinic acid salt represented by the formula (II) include, for example, methanedi (methylphosphinic acid) calcium (in the formula (II), R ³ = CH ₂ , R ⁴ = R ⁵ = CH ₃ , M = Ca), methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4-di (methylphosphinic acid) calcium (in formula (II), R ^{3 _{= C 6 H 4, R 4}} = R 5 = CH 3, M = Ca), benzene-1,4-di (methyl phosphinate) magnesium, benzene-1,4-di (methyl phosphinate) aluminum, benzene - 1, 4-di (methylphosphinic acid) zinc etc. are mentioned.

In the present invention, the flame retardant (c1) is preferably a phosphinic acid salt represented by the formula (I) from the viewpoint of flame retardancy and electrical properties, and more preferably R ¹ and R ² are each independently a straight chain. a C ₁ -C ₃ alkyl group, phosphinates M is represented by formula (I) is aluminum or zinc atom, in particular aluminum diethyl phosphinate, diethyl zinc phosphinates.

  The phosphinic acid salt represented by the above formula (I) and the diphosphinic acid salt represented by the above formula (II) are a predetermined phosphinic acid or diphosphinic acid, a metal carbonate containing a predetermined metal, and a metal hydroxide. Or it can manufacture in aqueous solution using a metal oxide. That is, it can be produced by mixing an aqueous solution of a predetermined phosphinic acid or diphosphinic acid with an aqueous solution of a metal carbonate, metal hydroxide or metal oxide containing a predetermined metal. The phosphinic acid salt represented by the formula (I) and the diphosphinic acid salt represented by the formula (II) exist essentially in the structure of the formula (I) or the formula (II), but depending on the reaction conditions Also included are polymeric phosphinates having a degree of condensation of 1-3.

  The flame retardant (c2) is a reaction product of phosphoric acid and melamine, a reaction product of cyanuric acid and melamine, or a mixture thereof.

  The reaction product of phosphoric acid and melamine is produced by the reaction between the hydroxyl group of phosphoric acid and the amino group of melamine, and is obtained by a substantially equimolar reaction of phosphoric acid and melamine. It is. In the present specification, unless otherwise specified, phosphoric acid is orthophosphoric acid, polyphosphoric acid obtained by dehydration condensation of orthophosphoric acid (for example, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, etc.), phosphorous acid, hypophosphorous acid. It means to include acid and metaphosphoric acid. Hereinafter, the reaction product of phosphoric acid and melamine shall be referred to as melamine phosphate. For example, melamine orthophosphate means a reaction product of orthophosphoric acid and melamine, and melamine polyphosphate is a reaction between polyphosphoric acid and melamine. It shall mean the product. Melamine phosphate is intended to include reaction products of various phosphoric acids and melamine, such as melamine orthophosphate, melamine polyphosphate (for example, melamine pyrophosphate, melamine triphosphate, melamine tetraphosphate, etc.) ), Melamine phosphite, melamine hypophosphite, melamine metaphosphate, and mixtures thereof. The preferred melamine phosphate is melamine orthophosphate, melamine polyphosphate, or mixtures thereof.

  There is no particular restriction on the production method of melamine phosphate, but usually, the prescribed phosphoric acid aqueous solution and melamine aqueous solution are mixed well to form both reaction products into fine particles, followed by filtration, washing and drying. Can be manufactured. In particular, melamine polyphosphate can be obtained by heat condensation of melamine orthophosphate in a nitrogen atmosphere.

  Melamine phosphate can also be obtained as a commercial product. For example, melamine polyphosphate (manufactured by Ciba Specialty Chemicals; Melapur 200/70), PMP-100 manufactured by Nissan Chemical Co., etc. can be used.

  As the melamine phosphate, a powder obtained by pulverizing to a particle size of 100 μm or less, preferably 50 μm or less, may be used in view of mechanical properties and appearance of a molded product obtained by molding the composition of the present invention. Use of a powder having a particle size of 0.5 to 20 μm is particularly preferable because not only high flame retardancy is exhibited but also the strength of a molded product is remarkably increased.

In this specification, the particle size uses a value measured by the following method.
It was dispersed in a 3% aqueous isopropanol solution and measured by optical correlation spectroscopy.

  A reaction product of cyanuric acid and melamine (hereinafter referred to as melamine cyanurate) is produced by a reaction between a hydroxyl group of cyanuric acid and an amino group of melamine, and substantially contains cyanuric acid and melamine. It is obtained by equimolar reaction.

  Although there is no restriction | limiting in particular in the manufacturing method of melamine cyanurate, For example, by mixing the aqueous solution of cyanuric acid and the aqueous solution of melamine, it is made to react, stirring at the temperature of about 70-100 degreeC, and filtering the obtained precipitate. Obtainable.

  Melamine cyanurate can also be obtained as a commercial product. For example, melamine cyanurate (manufactured by Ciba Specialty Chemicals; MC25), MC440 manufactured by Nissan Chemical Co., Ltd., MCA-CO manufactured by Mitsubishi Chemical Co., etc. can be used.

  As the melamine cyanurate, a powder obtained by pulverizing the particle size to 100 μm or less, preferably 50 μm or less, may be used from the viewpoint of mechanical properties and appearance of the molded product obtained by molding the composition of the present invention. Use of a powder having a particle size of 0.5 to 20 μm is particularly preferable because not only high flame retardancy is exhibited but also the strength of a molded product is remarkably increased.

  In the present invention, the flame retardant (c2) is preferably at least melamine phosphate, particularly melamine polyphosphate, more preferably melamine polyphosphate alone, from the viewpoint of flame retardancy.

From the viewpoint of flame retardancy, the preferred combination of flame retardant (c1) and flame retardant (c2) is:
A phosphinate-melamine phosphate represented by the formula (I),
-Phosphinate represented by formula (I)-melamine phosphate-melamine cyanurate,
A diphosphinate-melamine phosphate represented by the formula (II),
A diphosphinate-cyanuric acid melamine represented by the formula (II) and a diphosphinic acid salt-melamine phosphate-melamine cyanuric acid represented by the formula (II).
The most preferred combination is
A phosphinate-melamine polyphosphate represented by the formula (I), wherein R ¹ and R ² are each independently a linear C ₁ -C ₃ alkyl group and M is an aluminum or zinc atom;
A phosphinate-polyphosphate melamine-cyanuric acid represented by the formula (I), wherein R ¹ and R ² are each independently a linear C ₁ -C ₃ alkyl group and M is an aluminum or zinc atom melamine,
A formula wherein R ³ is a linear C ₁ -C ₃ alkylene group, R ⁴ and R ⁵ are each independently a linear C ₁ -C ₃ alkyl group, and M is an aluminum or zinc atom ( II) diphosphinic acid salt represented by melamine polyphosphate,
A formula wherein R ³ is a linear C ₁ -C ₃ alkylene group, R ⁴ and R ⁵ are each independently a linear C ₁ -C ₃ alkyl group, and M is an aluminum or zinc atom ( II) diphosphinic acid salt-melamine cyanurate, and R ³ is a linear C ₁ -C ₃ alkylene group, and R ⁴ and R ⁵ are each independently a linear C ₁ -C ₃ Diphosphinate-melamine polyphosphate-melamine cyanurate represented by the formula (II) which is an alkyl group and M is an aluminum or zinc atom.

  The content of the flame retardant (C), that is, the total content of the flame retardant (c1) and the flame retardant (c2) is 10 to 30% by mass, preferably 15 to 25% by mass with respect to the total amount of the composition. . If the content is too small, flame retardancy cannot be achieved sufficiently. If the content is too large, mechanical properties are deteriorated and mold contamination occurs, which is not preferable. Two or more kinds of flame retardants (c1) and (c2) may be used in combination, and in this case, the total amount thereof may be within the above range. As long as the objective of this invention is achieved, this invention does not prevent containing a flame retardant other than a flame retardant (c1) and a flame retardant (c2). When such other flame retardant is contained, the content of the other flame retardant is usually 20% by mass or less based on the total amount of the composition.

  The content ratio of the flame retardant (c1) and the flame retardant (c2) is 2 to 25 in terms of mass ratio (c1 / c2), preferably 4 to 20, and more preferably 5 to 20. If this content is too small, flame retardancy cannot be achieved sufficiently. When the content ratio is too large, the flame retardancy cannot be achieved or the mechanical properties are lowered, which is not preferable. When one or both of the flame retardants (c1) or (c2) are used in combination of two or more, the above-described content ratio may be achieved by their total amount.

  In the flame-retardant-reinforced polyamide resin composition of the present invention, other components such as colorants such as pigments and dyes, heat stabilizers, weather resistance improvers, nucleating agents, plasticizers, and the like, within a range that does not impair the purpose. Additives such as mold release agents and antistatic agents, and other resin polymers can be added. In particular, higher fatty acid metal salts, which are generally known as mold release agents, have the effect of suppressing gas generation during melting and kneading, and so-called eyes and can be suitably used. Examples of higher fatty acid metal salts include calcium, magnesium, sodium, zinc, aluminum, barium salts such as stearic acid, palmitic acid, oleic acid, aragic acid, behenic acid, and montanic acid. In particular, from the viewpoint of heat resistance, sodium montanate and calcium montanate can be preferably used.

  The form of the flame-retardant polyamide resin composition of the present invention is not particularly limited, and preferably has a form of a kneaded product obtained by melt-kneading at a temperature of 200 to 350 ° C. using a twin-screw extruder, From the viewpoint of more effectively achieving both flame retardancy and mechanical properties, it is more preferable that the material is obtained by sufficiently melting and mixing raw materials other than the inorganic filler, and then adding the inorganic filler and degassing under reduced pressure. The composition of the present invention can be obtained by known methods such as injection molding, extrusion molding, blow molding, etc., for example, various molded products for electrical / electronic and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, switches, etc. Etc. can be formed.

  Next, the present invention will be described more specifically with reference to examples. The materials used and the evaluation method fees in the examples and comparative examples are as follows.

Materials used;
(A) Polyamide resin polyamide 66; 24AD1 manufactured by Rhodia
Polyamide 66; 101 manufactured by DuPont
Polyamide 66; Unitika A142
Polyamide 6; Unitika 1015
(B) Inorganic reinforcing material glass fiber: CS03JA692 (average fiber diameter: 10 μm) manufactured by Asahi Fiber Glass Co., Ltd.
Wollastonite; Nyglos8 made by Nyco

(C) Flame retardant (c1): Phosphinate Aluminum diethylphosphinate (abbreviated as DEPAL)
(C1): Methanedi (methylphosphinic acid) zinc (MDEPZN)
(C2): Melapur 200/70 manufactured by Ciba Specialty Chemicals (abbreviated as PMP)
(C2): Melamine cyanurate MC25 manufactured by Ciba Specialty Chemicals (abbreviated as MC)

Evaluation methods;
a) Relative viscosity Measured under the conditions of a temperature of 25 ° C. and a concentration of 1 g / dl using 96 mass% concentrated sulfuric acid as a solvent. In addition, only the polyamide resin was used for the measurement.
b) Tensile strength and tensile elongation Measured according to ASTM D638.
c) Flexural strength and flexural modulus Measured according to ASTM D790.
d) Izod impact value Measured according to ASTM D256.

e) Flame retardancy Measured according to the method of UL94 (standard defined by Under Writers Laboratories Inc., USA). The thickness of the test piece was 1/32 inch (about 0.8 mm). V-0 is most desirable, which means that flame retardancy decreases in the order of V-1, V-2, and HB. The evaluation result within the allowable range in the present invention is V-0.

f) Tracking resistance As a test piece, a molded product having a size of 60 mm × 60 mm × 2 mm was used, and the resistance to the tracking tester HAT-500-3 manufactured by Hitachi Chemical Co., Ltd. % Ammonium chloride aqueous solution was dropped every 30 seconds, and the maximum voltage at which the test piece did not track and destroyed with 50 drops was determined. The higher this value, the better the tracking resistance.

Example 1
Biaxial so that polyamide 66 (24AD1) is 53.2% by mass, glass fiber is 30% by mass, DEPAL of flame retardant (c1) is 16% by mass, and PMP of flame retardant (c2) is 0.8% by mass. Using an extruder (TEM 37 manufactured by Toshiba Machine), a cylinder set temperature of 280 ° C., a screw rotation of 200 rpm, a discharge rate of 35 kg / h, other than glass fiber was introduced from the base, and the glass fiber was side fed and kneaded, It took out to strand shape, granulated with the cutter after cooling, and obtained the polyamide resin composition pellet. The obtained polyamide resin composition pellets were injection molded using an injection molding machine IS-100 manufactured by TOSHIBA MACHINE to obtain molded products of various shapes used in the above evaluation method. The results are shown in Table 1.

Examples 2-5 and Comparative Examples 1-6
Except for changing the blending ratio of each component as shown in Table 1, pellets were obtained in the same manner as in Example 1 to obtain molded products of various shapes. The results are shown in Table 1.

The flame-retardant-reinforced polyamide resin composition of the present invention can be suitably used for component materials such as connectors in the electrical / electronic field and electrical component parts in the automotive field.

Claims (6)

  (A) a polyamide resin, (B) an inorganic filler, and (C) a flame retardant, wherein the flame retardant is a reaction product of (c1) a phosphinate compound and (c2) phosphoric acid and melamine And / or a reaction product of cyanuric acid and melamine, the content ratio of which is 2 to 25 by mass ratio (c1 / c2), and the total content thereof is 10 to 30 based on the total amount of the composition A flame retardant reinforced polyamide resin composition, characterized in that the content is% by weight. The flame retardant reinforced polyamide resin composition according to claim 1, wherein the phosphinate compound is a phosphinate represented by the following formula (I) and / or a diphosphinate represented by the following formula (II). ;

(In the formula (I) and ^(II), an R ^1, R 2, ^{R 4} and ^{R 5} are each independently a straight chain or branched chain _C 1 _{-C 16} alkyl group or aryl group, and ^{R 1} R ² and R ⁴ and R ⁵ may form a ring with each other; R ³ is a linear or branched C _{1 to} C ₁₀ alkylene group, an arylene group, an alkylarylene group, or an arylalkylene group; M Is a calcium, magnesium, aluminum, or zinc atom; m is 2 or 3, n is 1 or 3, and x is 1 or 2; provided that mx = 2n in formula (II)) .   The flame retardant reinforced polyamide resin composition according to claim 1 or 2, wherein the reaction product of phosphoric acid and melamine is melamine orthophosphate, melamine polyphosphate, or a mixture thereof.   The flame retardant reinforced polyamide resin composition according to any one of claims 1 to 3, wherein the polyamide resin is polyamide 6, polyamide 66, or a mixture thereof.   The relative viscosity of the polyamide resin when measured under the conditions of a temperature of 25 ° C and a concentration of 1 g / dl using 96 mass% concentrated sulfuric acid as a solvent is 1.7 to 2.7, The flame retardant reinforced polyamide resin composition according to any one of the above. A molded article comprising the flame retardant reinforced polyamide resin composition according to any one of claims 1 to 5.