JP6129464B1 - Polyamide resin composition and molded body formed by molding the same - Google Patents

Abstract

A polyamide resin composition comprising a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine-based compound (C) having a hindered phenol structure, wherein the mass ratio of (A) to (B) (A / B) is 60/40 to 95/5, and the content of (C) is 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) and (B). A polyamide resin composition. [Selection figure] None

Description

  The present invention relates to a polyamide resin composition having flame retardancy.

  Polyamide is excellent in heat resistance and mechanical properties, and is used as many electrical / electronic parts and parts around automobile engines. Among these parts, polyamides used for electric and electronic parts are required to have higher flame retardancy.

As a method for imparting flame retardancy to polyamide, a method using a flame retardant is usually performed. In recent years, due to the increase in environmental awareness, halogen-based flame retardants have been avoided, and generally non-halogen-based flame retardants are used.
For example, Patent Document 1 discloses the use of a mixture of a reaction product of melamine and phosphoric acid, a phosphinic acid metal salt, and a metal compound as a non-halogen flame retardant, both of which are 1/16 inch. It is disclosed that the molded product satisfies the flame retardancy standard UL94V-0 standard. However, polyamide resin compositions containing phosphinic acid metal salts are highly corrosive to metals, and during melt processing, the metal parts such as extruder screws and dies, and molding machine screws and molds are severely worn. There was a problem of lack of mass productivity. In addition, this composition has a problem that a lot of gas is generated during the molding process, and dirt adheres to the mold.

  In addition, surface mounting is the mainstream for mounting electrical / electronic components, and the polyamide constituting the components is exposed to a high temperature of about 260 ° C. in the reflow process. Therefore, the use of a heat-resistant polyamide having a reflow resistance and a melting point of 270 ° C. or higher is increasing as a polyamide. Since the heat-resistant polyamide has a high processing temperature due to its high melting point, when the mixture containing the phosphinic acid metal salt or melamine described in Patent Document 1 is blended with the heat-resistant polyamide as a flame retardant, the above-mentioned metal corrosiveness is obtained during melt processing. However, there is a problem that the appearance of the obtained molded article is inferior due to decomposition of melamine or the mold is contaminated.

  As a method for suppressing metal corrosiveness and gas generation with respect to these problems, a technique of blending an auxiliary agent is disclosed. In Patent Document 2, calcium oxide is used, and in Patent Document 3, a salicylic acid derivative is used as an auxiliary agent. Is disclosed, Patent Document 4 discloses a technique of compounding an inorganic aluminum compound with polyamide having a specific structure, and Patent Document 5 discloses a technique of extruding under specific conditions.

JP 2007-023206 A Special table 2012-523469 International Publication No. 2011/007687 International Publication No. 2014/148519 International Publication No. 2009/107514

  The present invention solves the above-mentioned problems in a polyamide resin composition containing a metal salt of phosphinic acid and has excellent flame retardancy while suppressing metal corrosiveness during melt processing, and molding processing An object of the present invention is to provide a polyamide resin composition capable of reducing the generation of gas and the adhesion of dirt to a mold.

  As a result of intensive studies to solve the above problems, the inventors of the present invention improve flame retardancy by incorporating a specific amount of a specific compound in a polyamide resin composition containing a phosphinic acid metal salt. I found. Thereby, content of a phosphinic acid metal salt can be reduced, the problem resulting from a phosphinic acid metal salt can be solved, and it reached | attained this invention. That is, the gist of the present invention is as follows.

（２）ポリアミド（Ａ）の融点が２７０〜３５０℃であることを特徴とする（１）記載のポリアミド樹脂組成物。
（３）ポリアミド（Ａ）が、半芳香族ポリアミドと脂肪族ポリアミドとを含有し、質量比（半芳香族ポリアミド／脂肪族ポリアミド）が７０／３０〜４０／６０であることを特徴とする（１）記載のポリアミド樹脂組成物。
（４）ホスフィン酸金属塩（Ｂ）が、下記一般式（I）または（II）で表される化合物であることを特徴とする（１）〜（３）のいずれかに記載のポリアミド樹脂組成物。 (1) A polyamide resin composition comprising a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine compound (C) having a hindered phenol structure,
The mass ratio (A / B) of the polyamide (A) and the phosphinic acid metal salt (B) is 60/40 to 95/5,
Hydrazine compound having a hindered phenol structure (C) is a compound represented by the following formula (III), the content of that is, a total of 100 parts by weight of the polyamide (A) and the phosphinic acid metal salt (B) The polyamide resin composition is characterized by being 0.01 to 5 parts by mass.

(2) The polyamide resin composition according to (1), wherein the polyamide (A) has a melting point of 270 to 350 ° C.
(3) The polyamide (A) contains a semi-aromatic polyamide and an aliphatic polyamide, and has a mass ratio (semi-aromatic polyamide / aliphatic polyamide) of 70/30 to 40/60 ( 1) The polyamide resin composition as described.
(4) The polyamide resin composition according to any one of (1) to (3), wherein the phosphinic acid metal salt (B) is a compound represented by the following general formula (I) or (II): object.

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms or a phenyl group. R ³ is linear or branched. The chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group, and M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. is 2 or 3 .n, a, b are integers satisfying the relation of 2 × b = n × a. )

( 5 ) It further contains a reinforcing material (D), and the content thereof is 5 to 200 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). The polyamide resin composition according to any one of (1) to ( 4 ).
( 6 ) Further, at least one metal selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borates, metal stannates, fatty acid metal salts, hydrotalcite and derivatives thereof. The compound (E) is contained, and the content thereof is 0.01 to 8 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B) (1 The polyamide resin composition according to any one of ( 5 ) to ( 5 ).
( 7 ) The metal compound (E) contains a carbonate metal salt and a fatty acid metal salt, and the mass ratio (metal carbonate salt / fatty acid metal salt) is 90/10 to 30/70 ( 6). ) Polyamide resin composition.
( 8 ) A molded article obtained by molding the polyamide resin composition according to any one of (1) to ( 7 ) above.

  According to the present invention, it is possible to provide a flame-retardant polyamide resin composition in which the content of the metal phosphinate is reduced and the problems of metal corrosivity and gas generation caused by the content are solved. Since the content of the acid metal salt is reduced, a molded article having excellent mechanical properties can be provided.

It is a figure which shows the apparatus for evaluating metal corrosivity.

Hereinafter, the present invention will be described in detail.
The polyamide resin composition of the present invention contains a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine compound (C) having a hindered phenol structure.

In the present invention, the polyamide (A) includes, from the classification of polymerization methods, polycondensates of dicarboxylic acids and diamines, ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, and the like. From the classification, mention may be made of aliphatic polyamides, semi-aromatic polyamides, alicyclic polyamides, and copolymers thereof. As the polyamide (A), these polyamides may be used alone, or a copolymer or a mixture of two or more kinds of polyamides may be used.
Specific examples of the aliphatic polyamide include polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 612, polyamide 1010, and the like. Specific examples of semi-aromatic polyamides include polyamide 4T (T: terephthalic acid), polyamide 4I (I: isophthalic acid), polyamide 6I, polyamide 7T, polyamide 8T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T, polyamide MXD6. (MXD: metaxylylenediamine) and the like. Specific examples of the alicyclic polyamide include polyamide 6C (C: 1,4-cyclohexanedicarboxylic acid), polyamide 7C, polyamide 8C, polyamide 9C, polyamide 10C, polyamide 11C, and polyamide 12C. Further, as the copolymer, for example, when the diamine has 6 carbon atoms, PA66 / 6, PA6T / 6, PA6T / 12, PA6T / 46, PA6T / 66, PA6T / 610, PA6T / 612, PA6T / 6I, PA6T / 6I / 66, PA6T / M5T (M5: methylpentadiamine), PA6T / TM6T (TM6: 2,2,4- or 2,4,4-trimethylhexamethylenediamine), PA6T / MMCT (MMC: 4, 4'-methylenebis (2-methylcyclohexylamine)) and the like.

  The polyamide (A) preferably has a melting point of 270 ° C to 350 ° C. Since the polyamide (A) has a melting point of 270 ° C. or higher, it has heat resistance and can withstand a reflow process in which the maximum temperature is about 260 ° C. On the other hand, when the melting point of the polyamide (A) exceeds 350 ° C., the decomposition temperature of the amide bond is about 350 ° C., so that carbonization and decomposition may proceed during melt processing. As the polyamide (A) having heat resistance, polyamide 46, polyamide 6T, polyamide 9T, polyamide 10T, and copolymers thereof are preferable because of their high industrial versatility. Further, polyamide 6T, polyamide 9T, polyamide 10T, and copolymers thereof are more preferable because they are particularly excellent in reflow resistance from the viewpoint of high heat resistance and low water absorption, and polyamide 10T and copolymers thereof are particularly preferable. preferable.

  In the present invention, the semi-aromatic polyamide preferably contains a monocarboxylic acid component as a constituent component. The content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol%, and preferably 0.3 to 3.0 mol% with respect to all monomer components constituting the semiaromatic polyamide. More preferably, it is 0.3 to 2.5 mol%, more preferably 0.8 to 2.5 mol%. The semi-aromatic polyamide contains a monocarboxylic acid component within the above range, so that the molecular weight distribution at the time of polymerization can be reduced, the releasability at the time of molding processing can be improved, or the gas at the time of molding processing can be improved. The generation amount can be suppressed. On the other hand, when the content of the monocarboxylic acid component exceeds the above range, mechanical properties and flame retardancy may be deteriorated. In the present invention, the content of monocarboxylic acid refers to the proportion of the monocarboxylic acid residue in the semi-aromatic polyamide, that is, the proportion of the monocarboxylic acid from which the terminal hydroxyl group is eliminated.

  The semi-aromatic polyamide preferably contains a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, and more preferably contains a monocarboxylic acid having a molecular weight of 170 or more. When the molecular weight of the monocarboxylic acid is 140 or more, the releasability is improved, the amount of gas generated can be suppressed at the temperature during the molding process, and the molding fluidity can also be improved.

  Examples of the monocarboxylic acid component include aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, and aromatic monocarboxylic acid. Among them, the amount of generated gas of the polyamide-derived component is reduced, mold contamination is reduced, and release is performed. An aliphatic monocarboxylic acid is preferable because it can improve moldability.

Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferred because of its high versatility.
Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
Examples of the aromatic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid, and derivatives thereof. .

  The monocarboxylic acid component may be used alone or in combination. A monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination. In the present invention, the molecular weight of the monocarboxylic acid refers to the molecular weight of the starting monocarboxylic acid.

  In the present invention, the polyamide (A) preferably contains a semi-aromatic polyamide, and the semi-aromatic polyamide, as described above, has an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid having a molecular weight of 140 or more. It is comprised from an acid component, and it is preferable that content of a monocarboxylic acid component is 0.3-4.0 mol% with respect to all the monomer components which comprise a semi-aromatic polyamide.

In the present invention, the polyamide (A) preferably contains a semi-aromatic polyamide and an aliphatic polyamide, and the mass ratio of the semi-aromatic polyamide and the aliphatic polyamide (semi-aromatic polyamide / aliphatic polyamide) is 70/30 to 40/60. When the polyamide (A) contains an aliphatic polyamide in the above ratio together with a semi-aromatic polyamide, the polyamide (A) has heat resistance derived from the semi-aromatic polyamide and also has high fluidity derived from the aliphatic polyamide. It becomes possible to design an excellent resin composition. Furthermore, since the resin composition has high fluidity, the melt processing temperature can be lowered, and the shear heat generation of the resin can be suppressed, so that the metal corrosivity can be further suppressed.
The aliphatic polyamide contained together with the semi-aromatic polyamide preferably has a melting point of 200 to 300 ° C. Among the above-mentioned aliphatic polyamides, polyamide 6, polyamide 66 and polyamide 46 are preferred from the viewpoint of fluidity, and the polyamide 6. Polyamide 66 is more preferable

  In the present invention, the polyamide (A) preferably has a melt flow rate (MFR) of 1 to 200 g / 10 min when measured with a load of 1.2 kgf (melting point + 15 ° C.) according to JIS K7210. More preferably, it is -150g / 10min, and it is further more preferable that it is 20-100g / 10min. MFR can be used as an index of molding fluidity, and the higher the MFR value, the higher the fluidity. When the MFR of the polyamide (A) exceeds 200 g / 10 minutes, the mechanical properties of the resulting resin composition may be deteriorated. When the MFR of the polyamide (A) is less than 1 g / 10 minutes, the fluidity may be reduced. It is extremely low and may not be melt processed. When the polyamide (A) contains a plurality of polyamides having different melting points, the MFR of the polyamide (A) is measured at the melting point of the polyamide having the highest melting point + 15 ° C.

  The polyamide (A) can be produced using a conventionally known method such as a heat polymerization method or a solution polymerization method. Of these, the heat polymerization method is preferably used because it is industrially advantageous.

The polyamide resin composition of the present invention contains a phosphinic acid metal salt (B).
In the present invention, the mass ratio of polyamide (A) and phosphinic acid metal salt (B) (polyamide (A) / phosphinic acid metal salt (B)) must be 60/40 to 95/5. 70/30 to 92/8. When the ratio of the phosphinic acid metal salt (B) is less than 5% by mass, it is difficult to impart the required flame retardancy to the resin composition. On the other hand, when the ratio of the phosphinic acid metal salt (B) exceeds 40% by mass, the resin composition is excellent in flame retardancy, but the metal corrosivity becomes large and melt kneading may be difficult. Moreover, the molded product obtained may have insufficient mechanical properties.

  Examples of the phosphinic acid metal salt (B) of the present invention include phosphinic acid metal salts represented by the following general formula (I) and diphosphinic acid metal salts represented by the general formula (II).

In the formula, R ¹ , R ² , R ⁴ and R ⁵ are each independently required to be a linear or branched alkyl group having 1 to 16 carbon atoms or a phenyl group, and having 1 to 8 carbon atoms. Are preferably an alkyl group or a phenyl group, and are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, or a phenyl group. More preferred is an ethyl group. R ¹ and R ² and R ⁴ and R ⁵ may form a ring with each other.
R ³ is required to be a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group. Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, isopropylidene group, n-butylene group, tert-butylene group, n- A pentylene group, an n-octylene group, and an n-dodecylene group may be mentioned. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Examples of the alkylarylene group include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, and a tert-butylnaphthylene group. Examples of the arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group.
M represents a metal ion. Examples of the metal ions include calcium ions, aluminum ions, magnesium ions, and zinc ions. Aluminum ions and zinc ions are preferable, and aluminum ions are more preferable.
m and n represent the valence of the metal ion. m is 2 or 3. a represents the number of metal ions, b represents the number of diphosphinic acid ions, and n, a, and b are integers satisfying the relational expression “2 × b = n × a”.

  The phosphinic acid metal salt and diphosphinic acid metal salt are produced in an aqueous solution using the corresponding phosphinic acid and diphosphinic acid and metal carbonate, metal hydroxide or metal oxide, respectively, and usually exist as monomers. Depending on the reaction conditions, it may be present in the form of a polymeric phosphinate having a degree of condensation of 1-3.

  Specific examples of the phosphinic acid salt represented by the general formula (I) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphine. Magnesium oxide, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, methyl-n-propylphosphine Magnesium acetate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, calcium methylphenylphosphinate Arm, magnesium methylphenyl phosphinate, aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinic acid, diphenyl phosphinic acid zinc. Of these, aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and aluminum diethylphosphinate is more preferable because of excellent balance between flame retardancy and electrical characteristics.

  Moreover, as diphosphinic acid used for manufacture of a diphosphinic acid salt, methandi (methylphosphinic acid) and benzene-1,4-di (methylphosphinic acid) are mentioned, for example.

  Specific examples of the diphosphinic acid salt represented by the general formula (II) include, for example, calcium methanedi (methylphosphinate), methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, and methanedi (methylphosphinic acid) ) Zinc, benzene-1,4-di (methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4 -Di (methylphosphinic acid) zinc. Among these, methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable because of excellent balance between flame retardancy and electrical characteristics.

  Specific products of the phosphinic acid metal salt (B) include, for example, “Exolit OP1230”, “Exolit OP1240”, “Exolit OP1312”, “Exolit OP1314”, and “Exolit OP1400” manufactured by Clariant.

  The hydrazine compound (C) having a hindered phenol structure used in the present invention has both a hindered phenol structure having an effect of capturing peroxy radicals and a hydrazine structure chelating metal ions. Specific examples include compounds represented by the following formula (III).

  By combining the phosphinic acid metal salt (B) and the hydrazine compound (C) having a hindered phenol structure, the flame retardancy of the polyamide can be dramatically improved. Therefore, the compounding quantity of a phosphinic acid metal salt (B) can be reduced, and the metal corrosivity which is a subject of the polyamide resin composition containing a phosphinic acid metal salt can be suppressed.

  Specific products of the hydrazine-based compound (C) having a hindered phenol structure include, for example, “CDA-10” manufactured by Adeka, “IRGANOX MD 1024” manufactured by BASF.

  The content of the hydrazine compound (C) having a hindered phenol structure needs to be 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). It is preferable that it is 0.05-3 mass parts, and it is more preferable that it is 0.1-2 mass parts. If the content of the hydrazine-based compound (C) having a hindered phenol structure is less than 0.01 parts by mass, the effect of improving the flame retardancy cannot be obtained, while if the content exceeds 5 parts by mass, it is difficult. Not only does the fuel efficiency become saturated and no further improvement effect can be expected, but the resulting molded article may have insufficient mechanical strength.

  The polyamide resin composition of the present invention has dramatically improved flame retardancy. In addition, since the flame retardancy efficiency is high, the blending amount of the phosphinic acid metal salt (B) can be reduced while ensuring sufficient flame retardancy. Therefore, the metal corrosivity which was the subject of the polyamide resin composition containing a phosphinic acid metal salt (B) can be improved significantly. That is, it is possible to reduce corrosion and wear of the screw and die of the extruder during the melt extrusion process and the metal parts such as the screw and die of the molding machine during the melt molding process. The above-mentioned metal corrosivity in the polyamide resin composition containing the phosphinic acid metal salt (B) is particularly noticeable in melt processing at high temperatures, and is particularly a problem in heat-resistant polyamides having a high melting point. In the composition, a particularly excellent effect can be exhibited.

The polyamide resin composition of the present invention preferably further contains a reinforcing material (D). As reinforcing material (D), plate-like reinforcing materials such as talc, glass flake, mica, graphite, metal foil, carbon black, silicon carbide, silica, quartz powder, fused silica, glasses (glass beads, glass powder, milled) Spherical reinforcing materials such as glass fibers), silicates (calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, etc.), sulfates (calcium sulfate, barium sulfate, etc.), and fibrous reinforcing materials shown below Is mentioned. Since the improvement effect of mechanical characteristics is high, it is preferable to contain a fibrous reinforcing material.
The fibrous reinforcing material is not particularly limited. For example, glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoro Examples include ethylene fiber, kenaf fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, and basalt fiber. Among them, glass fiber, carbon fiber, and metal fiber are preferable because they have a high effect of improving mechanical properties, have heat resistance that can withstand the heating temperature during melt kneading with polyamide (A), and are easily available. The fibrous reinforcing material may be used alone or in combination.

  The glass fiber and the carbon fiber are preferably surface-treated with a silane coupling agent. The silane coupling agent may be dispersed in the sizing agent. Examples of the silane coupling agent include vinyl silanes, acrylic silanes, epoxy silanes, and amino silanes. Among them, amino silane cups have a high adhesion effect between polyamide (A) and glass fibers or carbon fibers. A ring agent is preferred.

The fiber length and fiber diameter of the fibrous reinforcing material are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm. When the fiber length of the fibrous reinforcing material is 0.1 to 7 mm, the resin composition can be reinforced without adversely affecting the moldability. The fiber diameter is preferably 3 to 20 μm, and more preferably 5 to 13 μm. When the fiber diameter is 3 to 20 μm, the resin composition can be reinforced without breaking during melt-kneading.
Examples of the cross-sectional shape of the fibrous reinforcing material include a circular shape, a rectangular shape, an elliptical shape, and other irregular cross-sections. A circular shape is preferable among them.

  When using the reinforcing material (D), the content of the reinforcing material (D) is preferably 5 to 200 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). The amount is more preferably 10 to 180 parts by mass, still more preferably 20 to 150 parts by mass, and particularly preferably 30 to 130 parts by mass. When the content of the reinforcing material (D) is less than 5 parts by mass, the effect of improving mechanical properties may be small. On the other hand, when the content exceeds 200 parts by mass, not only the improvement effect of the mechanical properties is saturated and the improvement effect cannot be further expected, but the workability at the time of melt-kneading is reduced, and the polyamide resin composition pellets are reduced. It may be difficult to obtain.

  The polyamide resin composition of the present invention preferably further contains a metal compound (E). As described above, the polyamide resin composition of the present invention contains the hydrazine compound (C) having a hindered phenol structure, thereby reducing the content of the phosphinic acid metal salt (B), and at the time of melt processing. Although metal corrosivity can be suppressed, metal corrosivity can be further suppressed by containing a metal compound (E).

  The content of the metal compound (E) is preferably 0.01 to 8 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). Part is preferable, and 0.1 to 2 parts by mass is more preferable. If the content of the metal compound (E) is less than 0.01 parts by mass, the effect of suppressing metal corrosivity cannot be obtained. On the other hand, when the content of the metal compound (E) exceeds 8 parts by mass, the effect of suppressing metal corrosivity is saturated, and not only a further suppression effect cannot be expected, but the mechanical strength of the obtained molded body is high. It may be insufficient.

In the present invention, the metal compound (E) is selected from the group consisting of metal oxide, metal hydroxide, carbonate metal salt, borate metal salt, metal stannate, fatty acid metal salt, hydrotalcite and derivatives thereof. Or a mixture of two or more.
Although the metal contained in a metal compound (E) is not specifically limited, For example, calcium, zinc, iron, aluminum, magnesium, silicon etc. are mentioned.
Examples of the metal oxide include zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina), magnesium oxide, and silicon oxide (silica).
Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and alumina hydrate (boehmite).
Examples of the metal carbonate include calcium carbonate and magnesium carbonate.
Examples of the boric acid metal salt include zinc borate, magnesium borate, calcium borate, aluminum borate and the like.
Examples of the metal stannate include zinc stannate.
Examples of the fatty acid metal salt include lithium salt, calcium salt, barium salt, zinc salt or aluminum salt of montanic acid, behenic acid or stearic acid.

  The metal compound (E) may be one kind of the above-mentioned compounds, or may be a mixture of two or more kinds. The metal compound (E) contains a carbonate metal salt and a fatty acid metal salt, and has a mass ratio (metal carbonate / When the fatty acid metal salt is 90/10 to 30/70, the resin composition is suppressed in metal corrosivity without lowering in flame retardancy.

  The polyamide resin composition of the present invention may further contain a flame retardant aid. Examples of the flame retardant aid include nitrogen-based flame retardants, nitrogen-phosphorous flame retardants, and inorganic flame retardants.

  Examples of the nitrogen-based flame retardant include melamine compounds, cyanuric acid or isocyanuric acid and melamine compounds. Specific examples of melamine compounds include melamine, melamine derivatives, compounds having a structure similar to melamine, condensates of melamine, and the like. Specifically, melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyano Examples thereof include compounds having a triazine skeleton such as melamine, benzoguanamine, acetoguanamine, succinoguanamine, melam, melem, methone and melon, and sulfates and melamine resins thereof. The salt of cyanuric acid or isocyanuric acid and a melamine compound is an equimolar reaction product of cyanuric acid or isocyanuric acid and a melamine compound.

Examples of the nitrogen-phosphorus flame retardant include adducts (melamine adducts) and phosphazene compounds formed from melamine or a condensation product thereof and a phosphorus compound.
Examples of the phosphorus compound constituting the melamine adduct include phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid. Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, and melam polyphosphate, among which melamine polyphosphate is preferable. The number of phosphorus is preferably 2 or more, and more preferably 10 or more.
Specific products of the phosphazene compound include, for example, “Ravitor FP-100”, “Ravitor FP-110” manufactured by Fushimi Pharmaceutical Co., Ltd., “SPS-100”, “SPB-100” manufactured by Otsuka Chemical Co., Ltd. .

  Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide and calcium hydroxide, zinc salts such as zinc borate and zinc phosphate, and calcium aluminate. Although many of these inorganic flame retardants overlap with the above metal compound (E), they may be blended for either purpose of improving flame retardancy or reducing metal corrosivity.

  The polyamide resin composition of the present invention can be further improved in stability and moldability by containing a phosphorus-based antioxidant.

  The phosphorus-based antioxidant may be either an inorganic compound or an organic compound. Examples of the phosphorus antioxidant include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, Phenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonyl phenyl phosphite, diphenyl isodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (" ADEKA STAB PEP-36 "), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (" ADEKA STAB PEP-24G "), tris (2,4-di-tert-butylphenyl) phosphite, Distearyl pentaerythritol Phosphite (“Adekastab PEP-8”), bis (nonylphenyl) pentaerythritol diphosphite (“Adekastab PEP-4C”), 1,1′-biphenyl-4,4′-diylbis [bisphosphonite (2 , 4-di-tert-butylphenyl)], tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene-di-phosphonite (“Hostanox P-EPQ”), tetra (tridecyl)- Examples include organophosphorus compounds such as 4,4'-isopropylidene diphenyl diphosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. Phosphorous antioxidants may be used alone or in combination.

  The phosphorus-based antioxidant easily mixes uniformly with the phosphinic acid metal salt (B) and prevents decomposition, so that flame retardancy can be improved. In addition, the phosphorus-based antioxidant can prevent the polyamide (A) from being decomposed and its molecular weight is reduced, and can improve operability, moldability, and mechanical properties during melt processing.

  It is preferable that content of phosphorus antioxidant is 0.1-3 mass parts with respect to a total of 100 mass parts of polyamide (A) and a phosphinic acid metal salt (B), and 0.1-1 mass part More preferably. By setting the content of the phosphorus-based antioxidant to 0.1 to 3 parts by mass, it is possible to release from the mold during molding without deteriorating stability, moldability and mechanical properties during extrusion. Can be improved, the clogging of the mold gas vent port can be suppressed, and the continuous injection moldability can be improved.

  If necessary, the polyamide resin composition of the present invention may further contain other stabilizers, colorants, antistatic agents, carbonization inhibitors, and other additives. Examples of the colorant include pigments such as titanium oxide, zinc oxide, and carbon black, and dyes such as nigrosine. Examples of the stabilizer include hindered phenol-based antioxidants, sulfur-based antioxidants, light stabilizers, heat stabilizers composed of copper compounds, and heat stabilizers composed of alcohols. The carbonization inhibitor is an additive that improves tracking resistance, and examples thereof include inorganic substances such as metal hydroxides and metal borate salts, and the above heat stabilizers.

  The method for producing the resin composition of the present invention is not particularly limited, but is added as necessary, such as polyamide (A), phosphinic acid metal salt (B), hydrazine-based compound (C) having a hindered phenol structure, and the like. A method in which a reinforcing material (D), a metal compound (E), other additives and the like are blended and melt-kneaded is preferable. Examples of the melt-kneading method include a method using a batch kneader such as Brabender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single screw extruder, a twin screw extruder and the like. The melt kneading temperature is selected from a region where the polyamide (A) melts and the polyamide (A) does not decompose. If the melt kneading temperature is too high, not only the polyamide (A) is decomposed but also the phosphinic acid metal salt (B) may be decomposed. Therefore, when the melting point of the polyamide (A) is Tm, (Tm− 20 ° C.) to (Tm + 50 ° C.).

  As a method of processing the polyamide resin composition of the present invention into various shapes, a method of extruding the molten mixture into a strand shape to form a pellet, a method of hot-cutting the molten mixture, underwater cutting to form a pellet, Examples include a method of extrusion cutting into a sheet shape, and a method of extrusion pulverization into a block shape to form a powder.

Examples of the molding method of the polyamide resin composition of the present invention include an injection molding method, an extrusion molding method, a blow molding method, and a sintering molding method. A molding method is preferred.
The injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine. The polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled to a predetermined shape and solidified, and then as a molded body from the mold. It is taken out. The resin temperature during injection molding is preferably heated and melted at a melting point (Tm) or higher of the polyamide (A), and more preferably less than (Tm + 50 ° C.).
In addition, when the polyamide resin composition is heated and melted, it is preferable to use sufficiently dried polyamide resin composition pellets. If the water content is large, the resin foams in the cylinder of the injection molding machine, and it may be difficult to obtain an optimal molded body. The moisture content of the polyamide resin composition pellets used for injection molding is preferably less than 0.3 parts by mass and more preferably less than 0.1 parts by mass with respect to 100 parts by mass of the polyamide resin composition.

The polyamide resin composition of the present invention is excellent in flame retardancy and can be molded while suppressing metal corrosiveness, and is used as a molded article for a wide range of applications such as automobile parts, electrical and electronic parts, sundries, civil engineering and building supplies. it can.
Examples of the automobile parts include a thermostat cover, an IGBT module member of an inverter, an insulator member, an exhaust finisher, a power device housing, an ECU housing, an ECU connector, a motor and a coil insulating material, and a cable covering material. Examples of electrical and electronic components include connectors, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, breakers, electromagnetic switches, holders, plugs, portable computers, word processors, and other electrical equipment. Examples include housings for housing parts, resistors, ICs, and LEDs. Among these, the polyamide resin composition of the present invention is particularly excellent in flame retardancy, and therefore can be suitably used for electric and electronic parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

1. Measuring method The physical properties of the polyamide and the polyamide resin composition were measured by the following methods. In the measurement of the resin composition of Example 30 containing two types of polyamides (A-1) and (A-5), the melting point of polyamide (A-1) having a high melting point was applied as the melting point.

(1) Melting point Using a differential scanning calorimeter DSC-7 (manufactured by PerkinElmer Co., Ltd.), the temperature was raised to 350 ° C. at a temperature rising rate of 20 ° C./min. The temperature was lowered to 25 ° C. in minutes, and further maintained at 25 ° C. for 5 minutes, and the top of the endothermic peak when the temperature was measured again at a rate of temperature rise of 20 ° C./min was defined as the melting point (Tm).

(2) Melt flow rate (MFR)
According to JIS K7210 (melting point + 15 ° C.), measurement was performed with a load of 1.2 kgf.
MFR can be used as an index of molding fluidity, and the higher the MFR value, the higher the fluidity.

(3) Mechanical properties The polyamide resin composition was injection molded under the conditions of cylinder temperature (melting point + 15 ° C.) and mold temperature (melting point −185 ° C.) using an injection molding machine S2000i-100B type (manufactured by FANUC). Thus, a test piece (dumbbell piece) was produced.
Using the obtained test piece, bending strength and bending elastic modulus were measured according to ISO178.
Bending strength and bending elastic modulus indicate that the larger the value, the better the mechanical properties.

(4) Flame retardance Polyamide resin composition is injection molded under conditions of cylinder temperature (melting point + 15 ° C.) and mold temperature (melting point−185 ° C.) using an injection molding machine CND15 (manufactured by Niigata Machine Techno Co., Ltd.). A test piece of 5 inches (127 mm) × 1/2 inch (12.7 mm) × 1/32 inch (0.79 mm) was produced.
Using the obtained test piece, flame retardancy was evaluated according to the standards of UL94 (standard defined by Under Writers Laboratories Inc., USA) shown in Table 1. When not satisfying any criteria, it was set as “not V-2”.
A shorter total afterflame time indicates better flame retardancy.

(5) Mold dirt Using an injection molding machine α-100iA (manufactured by FANUC), a shallow cup in one cycle 25 seconds under conditions of cylinder temperature (melting point + 25 ° C.) and mold temperature (melting point−185 ° C.) 500 shots of a shaped body (wall thickness 1.5 mm, outer diameter 40 mm, depth 30 mm) were continuously molded. After completion of molding, a gas vent having a depth of 4 μm and a width of 1 mm was visually confirmed, and mold contamination was evaluated according to the following criteria. ◎ and ○ were accepted.
◎: No clogging is observed at all ○: Some clogging is observed ×: Clogged completely

(6) Releasability By visually observing the presence or absence of the trace of the protruding pin of the molded body of the 401st to 500th shots when continuously molded in the above (5), counting the number of molded bodies having no pin trace, Release properties were evaluated.
The number of molded bodies without pin marks is preferably 90 or more, and more preferably 95 or more.

(7) Metal corrosiveness As shown in FIG. 1, a metal plate (MP) (material) used as a steel material for ordinary extruders, with a die (D) attached to a twin-screw kneading extruder (EX) (Ikegai PCM30) SUS630, 20 × 10 mm, thickness 5 mm, mass 7.8 g) was mounted on the top and bottom of the molten resin flow path (R), and a 1 mm gap was provided so that the molten resin was in contact over a width of 10 mm and a length of 20 mm. . A total of 25 kg of the polyamide resin composition was extruded into the gap under the conditions of the extruder barrel set temperature (melting point + 15 ° C.) and discharge of 7 kg / h. After the extrusion, the metal plate (MP) was removed, left in a furnace at 500 ° C. for 10 hours, the adhered resin was removed, the mass was measured, and the metal corrosivity was measured by the mass change before and after extrusion. The smaller the mass change, the greater the metal corrosivity.

2. Raw materials The raw materials used in Examples and Comparative Examples are shown below.

(1) Polyamide (A)
・ Polyamide (A-1)
4.70 kg of powdered terephthalic acid (TPA) as a dicarboxylic acid component, 0.32 kg of stearic acid (STA) as a monocarboxylic acid component, and 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst, The reactor was placed in a ribbon blender reactor and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under nitrogen sealing. Thereafter, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 2.98 kg of 1,10-decanediamine (DDA) 4.98 kg heated to 100 ° C. as a diamine component using a liquid injection device The reaction product was obtained by adding continuously (continuous liquid injection method) over 5 hours. The molar ratio of raw material monomers was TPA: DDA: STA = 48.5: 49.6: 1.9 (the equivalent ratio of functional groups of the raw material monomers was TPA: DDA: STA = 49.0: 50.0). : 1.0).
Subsequently, the obtained reaction product was polymerized by heating at 250 ° C. and a rotation speed of 30 rpm for 8 hours under a nitrogen stream in the same reaction apparatus to produce a polyamide powder.
Thereafter, the obtained polyamide powder was made into a strand shape using a biaxial kneader, the strand was passed through a water bath, cooled and solidified, and cut with a pelletizer to obtain polyamide (A-1) pellets.

-Polyamide (A-2) to (A-4)
Polyamides (A-2) to (A-4) were obtained in the same manner as the polyamide (A-1) except that the resin composition was changed as shown in Table 2.

Polyamide (A-5): Polyamide 66 (A125J manufactured by Unitika)
Polyamide (A-6): Polyamide 46 (TW300 manufactured by DSM)

  Table 2 shows the resin compositions and characteristic values of the polyamides (A-1) to (A-6).

(2) Phosphinic acid metal salt (B)
-B-1: Aluminum diethylphosphinate (Exolit OP1230 manufactured by Clariant)

(3) Hydrazine compounds having a hindered phenol structure (C)
C-1: N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine (CDA-10 manufactured by Adeka)

(4) Reinforcement material D-1: Glass fiber (03JAFT692 manufactured by Asahi Fiber Glass Co., Ltd.), average fiber diameter 10 μm, average fiber length 3 mm
D-2: Talc (Nihon Talc Co., Ltd. Microace K-1), average particle size 8 μm

(5) Metal compound E-1: Calcium oxide (Kanto Chemical Co., Ltd. deer first grade)
E-2: Hydrotalcite (DHT-4A-2 manufactured by Kyowa Chemical Industry Co., Ltd.)
E-3: Zinc stannate (Nippon Light Metal Co., Ltd., Flametard S)
E-4: Calcium carbonate (White White P-30 manufactured by Shiroishi Kogyo Co., Ltd.)
E-5: Barium stearate (Ba-St P manufactured by Nitto Kasei Kogyo Co., Ltd.)

(6) Phosphorous antioxidant F-1: Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite (Clariant's Hostanox P-EPQ)

(7) Triazole compound G-1: 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide (CDA-1 manufactured by Adeka)

Example 1
75 parts by mass of polyamide (A-1), 25 parts by mass of phosphinic acid metal salt (B-1), 1 part by mass of hydrazine compound (C-1) having a hindered phenol structure, 1 mass of metal compound (E-1) Part, 0.3 parts by mass of phosphorus-based antioxidant (F-1) are dry blended and weighed using a loss-in-weight continuous quantitative supply device CE-W-1 (manufactured by Kubota), screw diameter 26 mm , L / D50, the same direction twin screw extruder TEM26SS type (manufactured by Toshiba Machine Co., Ltd.) was supplied to the main supply port and melt-kneaded. In the middle, 45 parts by mass of the reinforcing material (D-1) was supplied from the side feeder and further kneaded. After taking the strand from the die, it was cooled and solidified by passing through a water tank, and cut with a pelletizer to obtain polyamide resin composition pellets. The barrel temperature of the extruder was set to (melting point -5 to + 15 ° C), screw rotation speed 250 rpm, and discharge rate 25 kg / h.

Examples 2-32 and comparative example Except having changed the composition of the polyamide resin composition as shown in Tables 3-4, operation similar to Example 1 was performed and the polyamide resin composition pellet was obtained. In addition, the resin composition pellet displayed in Comparative Example nC such as Comparative Example 1C has the same composition as the pellet of the resin composition of Example n except that it does not contain a hydrazine-based compound (C) having a hindered phenol structure. It is.

  Various evaluation tests were performed using the obtained polyamide resin composition pellets. The results are shown in Tables 3-4.

Since the resin compositions of the examples satisfy the requirements of the present invention and contain the hydrazine compound (C) having a hindered phenol structure, the comparative example does not contain the hydrazine compound (C) having a hindered phenol structure. As compared with the resin composition, flame retardancy was improved and metal corrosivity at high temperatures was suppressed.
In Examples 1 and 12 to 15, the resin composition was improved in flame retardancy by increasing the content of the hydrazine-based compound having a hindered phenol structure. As will be described later, the resin composition of Comparative Example 3 was excellent in flame retardancy by containing 45 parts by mass of a phosphinic acid metal salt, but was extremely high in metal corrosivity. The flame retardancy comparable to the flame retardancy obtained in Comparative Example 3 contains a hydrazine-based compound having a hindered phenol structure even when the content of the phosphinic acid metal salt is reduced to 25 to 40 parts by mass. (Examples 11 and 15) obtained in this way, in Examples containing a hydrazine-based compound having a hindered phenol structure, the content of phosphinic acid metal salt can be reduced, and metal corrosivity is suppressed. Became possible.
From the comparison of Examples 1 to 6, the resin composition of Examples 1, 2, and 4 containing a monocarboxylic acid having a molecular weight of 140 or more as the monocarboxylic acid component of the polyamide to be used has less mold contamination, The releasability was excellent. From the comparison between Example 1 and Example 3, the resin composition of Example 1 using an aliphatic monocarboxylic acid as the monocarboxylic acid component was more than Example 3 using an aromatic monocarboxylic acid. The releasability was excellent. From the comparison between Example 1 and Example 2, the resin composition of Example 1 using 1,10-decanediamine rather than the resin composition of Example 2 using 1,9-nonanediamine as the aliphatic diamine component. The thing was superior in mechanical properties.
Although the melting point is 285 ° C., the resin composition of Example 6 containing an aliphatic polyamide (A-6) having a high water absorption rate has 1 to 2 blisters in the test piece in the reflow resistance test. Occurrence was seen. However, the resin compositions of all other examples containing a semi-aromatic polyamide containing a terephthalic acid component and having a low water absorption were excellent in reflow resistance, and no change was observed in the appearance of the test piece. In the reflow resistance test, the test piece for flame retardancy evaluation was subjected to moisture absorption treatment at 85 ° C. × 85% RH for 168 hours, and then in an infrared heating type reflow furnace at 150 ° C. for 1 minute. The sample was heated, heated to 265 ° C. at a rate of 100 ° C./min, and held for 10 seconds.

From the comparison between Examples 1 and 21, the resin composition of Example 1 using glass fiber as a reinforcing material has better mechanical properties than the resin composition of Example 21 using plate-like talc. It was.
In the comparison of Examples 1, 22 to 30, the resin composition contained a metal compound, whereby suppression of metal corrosivity was observed. The resin compositions of Examples 29 and 30 in which the metal compound contains a metal carbonate and a fatty acid metal salt are more incombustible than the resin compositions of Examples 1, 27 and 28 containing one metal compound. It became possible to suppress the decrease in sex.
The resin composition of Example 30 has improved fluidity compared to the resin composition of Example 29 in which the polyamide contains only a semi-aromatic polyamide because the polyamide contains a semi-aromatic polyamide and an aliphatic polyamide. However, the shear heat generation of the resin was suppressed, and the metal corrosiveness could be further suppressed, and the resin had reflow resistance despite containing the aliphatic polyamide.
In the comparison between Examples 1 and 31, the resin composition was improved in mechanical properties and releasability by containing a phosphorus-based antioxidant.
The resin compositions of Examples 7 and 26 have a flame retardancy of V-2, the resin composition of Example 8 has a flame retardancy of V-1, and is flame retardant as compared with the resin compositions of other examples. However, the metal corrosivity was greatly suppressed.

The resin compositions of Comparative Examples 1 and 2 were inferior in flame retardancy because they did not contain phosphinic acid metal salt or the content thereof was small.
Since the resin composition of Comparative Example 3 had a high content of phosphinic acid metal salt, it was excellent in flame retardancy, but the metal corrosivity was remarkably increased. In Comparative Examples 4 to 6, when the resin composition contained a hydrazine-based compound having a hindered phenol structure, the flame retardancy was further improved, but the metal corrosivity was not suppressed. In Comparative Example 7, when the content of the phosphinic acid metal salt was further increased in the resin composition, the strands could not be taken out during melt kneading, and the resin composition pellets could not be collected.
Since the resin composition of Comparative Example 8 contained a large amount of a hydrazine compound having a hindered phenol structure, the mechanical properties were lower than those of Examples 1 and 12 to 15 and the effect of improving flame retardancy was saturated. Was.
Since the resin composition of Comparative Example 9 used a triazole compound having a hydrazine structure in the ring but not having a hindered phenol structure in place of the hydrazine compound having a hindered phenol structure, Example 1 was used. Compared with the resin composition, the effect of improving flame retardancy was not observed.

EX: twin-screw kneading extruder D: die MP: metal plate R: flow path of molten resin

Claims (8)

A polyamide resin composition comprising a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine compound (C) having a hindered phenol structure,
The mass ratio (A / B) of the polyamide (A) and the phosphinic acid metal salt (B) is 60/40 to 95/5,
Hydrazine compound having a hindered phenol structure (C) is a compound represented by the following formula (III), the content of that is, a total of 100 parts by weight of the polyamide (A) and the phosphinic acid metal salt (B) The polyamide resin composition is characterized by being 0.01 to 5 parts by mass.

  The polyamide resin composition according to claim 1, wherein the melting point of the polyamide (A) is 270 to 350 ° C.   The polyamide (A) contains a semi-aromatic polyamide and an aliphatic polyamide, and the mass ratio (semi-aromatic polyamide / aliphatic polyamide) is 70/30 to 40/60. Polyamide resin composition. The polyamide resin composition according to claim 1, wherein the phosphinic acid metal salt (B) is a compound represented by the following general formula (I) or (II).

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms or a phenyl group. R ³ is linear or branched. The chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group, and M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. Is 2 or 3. n, a, and b are integers satisfying the relational expression 2 × b = n × a.) The reinforcing material (D) is further contained, and the content thereof is 5 to 200 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). The polyamide resin composition in any one of 1-4 . Further, at least one metal compound (E) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, borate metal salts, metal stannates, fatty acid metal salts, hydrotalcite and derivatives thereof. ) contains, the content thereof, per 100 parts by weight of the polyamide (a) and the phosphinic acid metal salt (B),. 1 to claim characterized in that it is a 0.01-8 parts by weight 5 The polyamide resin composition according to any one of the above. Metal compound (E) is contained and carbonate metal salt and a fatty acid metal salt, the weight ratio (metal carbonate / fatty acid metal salt) of claim 6, wherein the 90 / 10-30 / 70 Polyamide resin composition. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 7 .

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