JP6889906B2 - Polyamide resin composition and molded article obtained by molding the polyamide resin composition - Google Patents

Description

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

Polyamide has excellent heat resistance and mechanical properties, and is used as many electric / electronic parts and parts around automobile engines. Among these parts, polyamides used in electrical and electronic parts are required to have even 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 heightened environmental awareness, halogen-based flame retardants have been avoided, and non-halogen flame retardants are generally used.
For example, Patent Document 1 discloses that a mixture of a reaction product of melamine and phosphoric acid, a metal salt of phosphinic acid, and a metal compound is used as a non-halogen flame retardant, both of which are 1/16 inch. It is disclosed that the molded product satisfies the flame retardant standard UL94V-0 standard. However, the polyamide resin composition containing a metal salt of phosphinic acid is highly corrosive to metals and violently wears metal parts such as screws and dies of extruders and screws and dies of molding machines during melt processing. , There was a problem of lack of mass productivity. Further, this composition has a problem that a large amount of gas is generated during the molding process and dirt adheres to the mold.

In addition, surface mounting is the mainstream for mounting electrical and electronic components, and in the reflow process, the polyamides that make up the components are exposed to a high temperature of about 260 ° C. at the maximum temperature. Therefore, there are many cases where it is necessary to use a heat-resistant polyamide having a melting point of 270 ° C. or higher, which has reflow resistance, as the polyamide. Since the heat-resistant polyamide has a high processing temperature due to its high melting point, when a mixture containing a metal salt of phosphinic acid, melamine, etc. described in Patent Document 1 is blended with the heat-resistant polyamide as a flame retardant, the above-mentioned metal corrosiveness occurs during melt processing. There is also a problem that the melamine is further large, and there is a problem that the appearance of the obtained molded product is deteriorated or the mold is contaminated due to the decomposition of melamine.

To solve these problems, a technique for blending an auxiliary agent is disclosed as a method for suppressing metal corrosiveness and gas generation. Patent Document 2 uses calcium oxide, and Patent Document 3 uses a salicylic acid derivative as an auxiliary agent. Patent Document 4 discloses a technique for blending an inorganic aluminum compound with a polyamide having a specific structure, and Patent Document 5 discloses a technique for extruding under specific conditions.

JP-A-2007-0232206 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 while having excellent flame retardancy, metal corrosiveness during melt processing is suppressed, and molding processing is performed. It is an object of the present invention to provide a polyamide resin composition capable of reducing the generation of gas and the adhesion of stains to a mold at the time.

As a result of intensive studies to solve the above problems, the present inventors have improved flame retardancy by adding a specific amount of a specific compound to a polyamide resin composition containing a metal salt of phosphinic acid. I found. As a result, the content of the metal phosphinic acid salt can be reduced to solve the problem caused by the metal phosphinic acid salt, and the present invention has been reached. That is, the gist of the present invention is as follows.

(1) A polyamide resin composition containing a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine-based compound (C) having a hindered phenol structure.
The mass ratio (A / B) of the polyamide (A) to the metal phosphinic acid salt (B) is 60/40 to 95/5.
The content of the hydrazine-based compound (C) having a hindered phenol structure is 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). Polyamide resin composition.
(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). 1) The above-mentioned polyamide resin composition.
(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). Stuff.

(In the formula, R ¹ , R ² , R ⁴ and R ⁵ independently represent an alkyl group or a phenyl group having 1 to 16 carbon atoms in a linear or branched chain, respectively. R ³ is a linear or branched chain or branched chain. It represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkyl arylene group. 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 relational expression of 2 × b = n × a. )

( 5 ) Further, the reinforcing material (D) is 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 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 borate salts, metal oxalate salts, metal fatty acid salts, hydrotalcites and derivatives thereof. The compound (E) is contained, and the content thereof is 0.01 to 8 parts by mass with respect to a total of 100 parts by mass of the polyamide (A) and the phosphinic acid metal salt (B) (1). )-( 5 ). The polyamide resin composition according to any one of (5).
( 7 ) The metal compound (E) contains a metal carbonate and a fatty acid metal salt, and has a mass ratio (metal carbonate / fatty acid metal salt) of 90/10 to 30/70 ( 6). ) The above-mentioned polyamide resin composition.
( 8 ) A molded product 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 salt of phosphinic acid is reduced to solve the problems of metal corrosiveness and gas generation caused by the content, and phosphine. Since the content of the acid metal salt is reduced, it is possible to provide a molded product having excellent mechanical properties.

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

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

In the present invention, the polyamide (A) includes a polycondensate of dicarboxylic acid and diamine, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and the like according to the classification of the polymerization method. Classification includes 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, and polyamide 1010. Specific examples of the semi-aromatic polyamide 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: metaxylylene diamine) 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 number of carbon atoms of the diamine is 6, 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 the melt processing. As the heat-resistant polyamide (A), 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 their copolymers 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 its copolymer 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%, preferably 0.3 to 3.0 mol%, based on all the monomer components constituting the semi-aromatic polyamide. More preferably, it is more preferably 0.3 to 2.5 mol%, and particularly preferably 0.8 to 2.5 mol%. By containing a monocarboxylic acid component within the above range, the semi-aromatic polyamide can reduce the molecular weight distribution during polymerization, improve the releasability during molding, and can be used for gas during molding. The amount of generation can be suppressed. On the other hand, if the content of the monocarboxylic acid component exceeds the above range, the mechanical properties and flame retardancy may deteriorate. In the present invention, the content of the monocarboxylic acid refers to the ratio of the residue of the monocarboxylic acid in the semi-aromatic polyamide, that is, the monocarboxylic acid desorbed from the terminal hydroxyl group.

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 mold releasability can be improved, the amount of gas generated at the temperature during molding can be suppressed, 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 gas generated by the polyamide-derived component is reduced, mold stains are reduced, and separation is performed. Aliphatic monocarboxylic acids are preferred because they can improve moldability.

Examples of aliphatic monocarboxylic acids 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 preferable 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 aromatic monocarboxylic acids 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. Further, 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 raw material monocarboxylic acid.

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

Further, 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 to the aliphatic polyamide (semi-aromatic polyamide / aliphatic polyamide) is , 70/30 to 40/60 is preferable. When the polyamide (A) contains an aliphatic polyamide in the above ratio together with the semi-aromatic polyamide, it has a balance having high fluidity derived from the aliphatic polyamide while having heat resistance derived from the semi-aromatic polyamide. It is possible to design a good resin composition. Furthermore, since the resin composition has high fluidity, the melting processing temperature can be lowered, and the shear heat generation of the resin can be suppressed, so that the metal corrosiveness 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 preferable, and polyamide 6 is preferable from the viewpoint of fluidity. 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 minutes when measured under a load of 1.2 kgf (melting point + 15 ° C.) according to JIS K7210. It is more preferably ~ 150 g / 10 minutes, and even more preferably 20 to 100 g / 10 minutes. The MFR can be used as an index of molding fluidity, and the higher the MFR value, the higher the fluidity. If the MFR of the polyamide (A) exceeds 200 g / 10 minutes, the mechanical properties of the obtained resin composition may deteriorate, and if the MFR of the polyamide (A) is less than 1 g / 10 minutes, the fluidity becomes low. It is extremely low and may not be melted. 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 by using a conventionally known method of heat polymerization method or solution polymerization method. Among them, the heat polymerization method is preferably used because it is industrially advantageous.

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

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

In the formula, R ¹ , R ² , R ⁴ and R ⁵ each need to be an alkyl group or a phenyl group having 1 to 16 carbon atoms in a straight chain or a branched chain, respectively, and have 1 to 8 carbon atoms. Is preferably an alkyl group or a phenyl group, and is 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 preferably, it is more preferably an ethyl group. R ¹ and R ² and R ⁴ and R ⁵ may form rings with each other.
R ³ needs 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 alkylene group having 1 to 10 carbon atoms in the linear or branched chain include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, an n-butylene group, a tert-butylene group and an n-. Examples thereof include a pentylene group, an n-octylene group and an n-dodecylene group. 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 ion include calcium ion, aluminum ion, magnesium ion and zinc ion, and aluminum ion and zinc ion are preferable, and aluminum ion is 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 diphosphane ions, and n, a, and b are integers satisfying the relational expression of “2 × b = n × a”.

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

Specific examples of the phosphinate represented by the above general formula (I) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphine, ethylmethylphosphine. Magnesium acid, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphine, methyl-n-propylphosphine Magnesium Acid, Aluminum Methyl-n-propylphosphinate, Zinc Methyl-n-propylphosphinate, Calcium Methylphenylphosphinate, Magnesium Methylphenylphosphinate, Aluminum Methylphenylphosphinate, Zinc Methylphenylphosphinate, Calcium diphenylphosphinate, Examples thereof include magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. Among them, aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and aluminum diethylphosphinate is more preferable, because they are excellent in flame retardancy and an excellent balance of electrical characteristics.

Examples of the diphosphinic acid used for producing the diphosphinate include methanedi (methylphosphinic acid) and benzene-1,4-di (methylphosphinic acid).

Specific examples of the diphosphinate represented by the above general formula (II) include calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), 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 can be mentioned. Of these, methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable because they have an excellent balance of flame retardancy and electrical characteristics.

Specific products of the phosphinic acid metal salt (B) include, for example, Clariant's "Exolit OP1230", "Exolit OP1240", "Exolit OP1312", "Exolit OP1314", and "Exolit OP1400".

The hydrazine-based 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. Specifically, a compound represented by the following formula (III) can be mentioned.

By combining the phosphinic acid metal salt (B) and the hydrazine-based compound (C) having a hindered phenol structure, the flame retardancy of the polyamide can be dramatically improved. Therefore, the blending amount of the phosphinic acid metal salt (B) can be reduced, and the metal corrosiveness which is a problem of the polyamide resin composition containing the 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 Corporation and "IRGANOX MD 1024" manufactured by BAS.

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 preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass. If the content of the hydrazine compound (C) having a hindered phenol structure is less than 0.01 parts by mass, the effect of improving the flame retardancy efficiency cannot be obtained, while if the content exceeds 5 parts by mass, it is difficult. Not only is the fuel efficiency saturated and no further improvement effect can be expected, but the resulting molded product may have insufficient mechanical strength.

The polyamide resin composition of the present invention has dramatically improved flame retardancy. Not only that, 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 corrosiveness, which has been a problem of the polyamide resin composition containing the phosphinic acid metal salt (B), can be significantly improved. That is, it is possible to reduce the corrosion and wear of metal parts such as the screw and die of the extruder during the melt extrusion process and the screw and mold of the molding machine during the melt extrusion process. The metal corrosiveness of the polyamide resin composition containing the metal phosphinic acid salt (B) was particularly remarkable in the melt processing at a high temperature, and was particularly problematic in the heat-resistant polyamide having a high melting point. Therefore, the resin containing the heat-resistant polyamide. A particularly excellent effect can be exhibited in the composition.

The polyamide resin composition of the present invention preferably further contains a reinforcing material (D). The reinforcing material (D) includes plate-shaped reinforcing materials such as talc, glass flakes, mica, graphite, and metal foil, carbon black, silicon carbide, silica, quartz powder, molten silica, and glass (glass beads, glass powder, milled). Spherical reinforcing materials such as glass fiber), silicates (calcium silicate, aluminum silicate, kaolin, clay, diatomaceous soil, etc.), sulfates (calcium sulfate, barium sulfate, etc.), and fibrous reinforcing materials shown below. Can be mentioned. It is preferable to contain a fibrous reinforcing material because it has a high effect of improving mechanical properties.
The fibrous reinforcing material is not particularly limited, but for example, glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, total aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoro. Examples thereof include ethylene fiber, kenaf fiber, bamboo fiber, hemp fiber, bagas fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless fiber, steel fiber, ceramics fiber, and genbuiwa 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 at the time of melt-kneading with polyamide (A), and are easily available. The fibrous reinforcing material may be used alone or in combination.

The glass fiber and 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 vinylsilane-based, acrylicsilane-based, epoxysilane-based, and aminosilane-based, and among them, the aminosilane-based cup has a high adhesion effect between the polyamide (A) and the glass fiber or carbon fiber. Ring agents are 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, more preferably 0.5 to 6 mm. Since 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, more preferably 5 to 13 μm. Since 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-sectional shapes, and a circular shape is preferable.

When the reinforcing material (D) is used, the content of the reinforcing material (D) is preferably 5 to 200 parts by mass with respect to a total of 100 parts by mass of the polyamide (A) and the metal phosphinic acid salt (B). It is more preferably 10 to 180 parts by mass, further preferably 20 to 150 parts by mass, and particularly preferably 30 to 130 parts by mass. If the content of the reinforcing material (D) is less than 5 parts by mass, the effect of improving the mechanical properties may be small. On the other hand, when the content exceeds 200 parts by mass, not only the effect of improving the mechanical properties is saturated and no further improvement effect can be expected, but also the workability at the time of melt-kneading is lowered, and the pellet of the polyamide resin composition is formed. It can be difficult to obtain.

The polyamide resin composition of the present invention preferably further contains the metal compound (E). As described above, the polyamide resin composition of the present invention contains the hydrazine-based compound (C) having a hindered phenol structure to reduce the content of the phosphinic acid metal salt (B) and is used during melt processing. Although the metal corrosiveness can be suppressed, the metal corrosiveness can be further suppressed by containing the metal compound (E).

The content of the metal compound (E) is preferably 0.01 to 8 parts by mass, preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total of the polyamide (A) and the phosphinic acid metal salt (B). The amount is preferably 0.1 to 2 parts by mass, more preferably 0.1 to 2 parts by mass. If the content of the metal compound (E) is less than 0.01 parts by mass, the effect of suppressing metal corrosiveness 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 corrosiveness is saturated, and not only the effect of suppressing metal corrosiveness cannot be expected, but also the mechanical strength of the obtained molded product is increased. It may be insufficient.

In the present invention, the metal compound (E) is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate salts, metal tinic acid salts, fatty acid metal salts, hydrotalcites and derivatives thereof. It is one kind or a mixture of two or more kinds.
The metal contained in the metal compound (E) is not particularly limited, and examples thereof include calcium, zinc, iron, aluminum, magnesium, and silicon.
Examples of the metal oxide include zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina), magnesium oxide, silicon oxide (silica) and the like.
Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, alumina hydrate (boehmite) and the like.
Examples of the metal carbonate include calcium carbonate, magnesium carbonate and the like.
Examples of the metal borate salt include zinc borate, magnesium borate, calcium borate, aluminum borate and the like.
Examples of the metal tin sulphate salt include zinc succinate.
Examples of the fatty acid metal salt include a lithium salt, a calcium salt, a barium salt, a zinc salt and an aluminum salt of montanic acid, behenic acid or stearic acid.

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

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

Examples of the nitrogen-based flame retardant include a melamine-based compound, cyanuric acid, or a salt of isocyanuric acid and a melamine compound. Specific examples of melamine-based compounds include melamine, melamine derivatives, compounds having a structure similar to melamine, and condensates of melamine. Specifically, melamine, ammeline, ammeline, formoguanamine, guanyl melamine, and 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 an adduct (melamine adduct) formed from melamine or a condensation product thereof and a phosphorus compound, and a phosphazene 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, polyphosphoric acid and the like. Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, and melamine polyphosphate, and among them, 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, "Rabbitl FP-100" and "Rabbitl FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd., "SPS-100" and "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 aluminates. Many of these inorganic flame retardants overlap with the metal compound (E), but they may be blended for either purpose of improving flame retardancy or reducing metal corrosiveness.

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 phosphoric acid antioxidant include monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite and other inorganic phosphates, and birds. Phosphate Phosphate, Trioctadecylphosphate, Tridecylphosphate, Trinonylphenylphosphate, Diphenylisodecylphosphate, Bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphate (" Adecastab PEP-36 "), Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphate (" Adecastab PEP-24G "), Tris (2,4-di-tert-butylphenyl) phosphate, Distearyl pentaerythritol diphosphate ("Adecastab PEP-8"), bis (nonylphenyl) pentaerythritol diphosphate ("Adecastab PEP-4C"), 1,1'-biphenyl-4,4'-diylbis [sub Bisphosphonate (2,4-di-tert-butylphenyl)], Tetrax (2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite ("Hostanox P-EPQ"), Included are organophosphorus compounds such as tetra (tridecyl) -4,4'-isopropyridene diphenyldiphosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite. The phosphorus-based antioxidant may be used alone or in combination.

The phosphorus-based antioxidant is easily mixed 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 decomposition of the polyamide (A) and decrease in molecular weight, and can improve operability, moldability, and mechanical properties during melt processing.

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

If necessary, other additives such as stabilizers, colorants, antistatic agents, and carbonization inhibitors may be further added to the polyamide resin composition of the present invention. Examples of the colorant include pigments such as titanium oxide, zinc oxide and carbon black, and dyes such as niglosin. Examples of the stabilizer include a hindered phenol-based antioxidant, a sulfur-based antioxidant, a light stabilizer, a heat stabilizer made of a copper compound, a heat stabilizer made of alcohols, and the like. 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-mentioned heat stabilizers.

The method for producing the resin composition of the present invention is not particularly limited, but a polyamide (A), a phosphinic acid metal salt (B), a hydrazine-based compound (C) having a hindered phenol structure, and, if necessary, are added. A method of blending a reinforcing material (D), a metal compound (E), other additives, and the like and melt-kneading is preferable. Examples of the melt-kneading method include a method using a batch kneader such as lavender, 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 the region where the polyamide (A) is melted and the polyamide (A) is not decomposed. If the melt-kneading temperature is too high, not only the polyamide (A) may be decomposed, but also the phosphinic acid metal salt (B) may be decomposed. Therefore, assuming that the melting point of the polyamide (A) is Tm, (Tm-). 20 ° C.) to (Tm + 50 ° C.) is preferable.

Examples of the method for processing the polyamide resin composition of the present invention into various shapes include a method of extruding the molten mixture into a strand shape into a pellet shape, a method of hot-cutting and underwater-cutting the molten mixture into a pellet shape, and a method of forming a pellet shape. Examples thereof include a method of extruding into a sheet and cutting, and a method of extruding into a block and crushing 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, which have a large effect of improving mechanical properties and moldability. The molding method is preferable.
The injection molding machine is not particularly limited, and examples thereof include a screw in-line 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 and solidified in a predetermined shape, and then molded from the mold. Taken out. The resin temperature at the time of injection molding is preferably heat-melted at a temperature equal to or higher than the melting point (Tm) of the polyamide (A), and more preferably lower than (Tm + 50 ° C.).
When the polyamide resin composition is heated and melted, it is preferable to use sufficiently dried polyamide resin composition pellets. If the amount of water contained is large, the resin may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimum molded product. The water 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 has excellent flame retardancy and can be molded while suppressing metal corrosiveness, and can be used as a molded product for a wide range of applications such as automobile parts, electrical and electronic parts, miscellaneous goods, and civil engineering and construction supplies. it can.
Examples of automobile parts include thermostat covers, inverter IGBT module members, insulator members, exhaust finishers, power device housings, ECU housings, ECU connectors, motor and coil insulating materials, and cable covering materials. Electrical and electronic components include, for example, connectors, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, breakers, electromagnetic switches, holders, plugs, portable personal computers, word processors, and other electrical equipment. Examples include housing components, resistors, ICs, and LED housings. Above all, the polyamide resin composition of the present invention is particularly excellent in flame retardancy, and therefore can be suitably used for electrical and electronic parts.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Measurement method The physical properties of the polyamide and polyamide resin composition were measured by the following methods. In the measurement of the resin composition of Example 30 containing two kinds of polyamides (A-1) and (A-5), the melting point of the 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), the temperature is raised to 350 ° C at a heating rate of 20 ° C / min, held at 350 ° C for 5 minutes, and the temperature is lowered at a rate of 20 ° C / min. The temperature was lowered to 25 ° C. in minutes, and after holding at 25 ° C. for 5 minutes, the top of the heat absorption peak when the temperature was raised again at a temperature rising rate of 20 ° C./min was defined as the melting point (Tm).

(2) Melt flow rate (MFR)
According to JIS K7210 (melting point + 15 ° C.), the measurement was carried out under a load of 1.2 kgf.
The 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 is injection molded using an injection molding machine S2000i-100B (manufactured by FANUC) under the conditions of cylinder temperature (melting point + 15 ° C) and mold temperature (melting point-185 ° C). Then, a test piece (dumbbell piece) was prepared.
Using the obtained test piece, bending strength and flexural modulus were measured according to ISO178.
As for the bending strength and flexural modulus, the larger the numerical value, the better the mechanical properties.

(4) The flame-retardant polyamide resin composition is injection-molded using an injection molding machine CND15 (manufactured by Niigata Machine Techno Co., Ltd.) under the conditions of cylinder temperature (melting point + 15 ° C.) and mold temperature (melting point-185 ° C.). A test piece of 5, 5 inch (127 mm) × 1/2 inch (12.7 mm) × 1/32 inch (0.79 mm) was prepared.
Using the obtained test pieces, the flame retardancy was evaluated according to the UL94 (standard defined by the US Under Writer's Laboratories Inc.) standard shown in Table 1. When none of the criteria was met, it was set as "not V-2".
The shorter the total residual flame time, the better the flame retardancy.

(5) Mold dirt Using an injection molding machine α-100iA (manufactured by FANUC), a shallow cup is used in 25 seconds per cycle under the conditions of cylinder temperature (melting point + 25 ° C) and mold temperature (melting point-185 ° C). A molded product having a shape (thickness: 1.5 mm, outer diameter: 40 mm, depth: 30 mm) was continuously molded for 500 shots. After the molding was completed, 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 seen ○: Partially clogged ×: Completely clogged

(6) Releasability The presence or absence of marks on the protruding pins of the 401 to 500 shots of the molded body when continuously molded in (5) above was visually observed, and the number of molded bodies without pin marks was counted. The releasability was evaluated.
The number of molded products without pin marks is preferably 90 or more, and more preferably 95 or more.

(7) Metal Corrosion As shown in FIG. 1, a die (D) is attached to a twin-screw kneading extruder (EX) (PCM30 manufactured by Ikekai Co., Ltd.), and a metal plate (MP) (material) normally used as a steel material for an extruder. SUS630, 20 × 10 mm, thickness 5 mm, mass 7.8 g) were attached above and below the flow path (R) of the molten resin, and a gap of 1 mm 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 extrusion, the metal plate (MP) was removed and left in a furnace at 500 ° C. for 10 hours to remove the adhering resin, and then the mass was measured, and the metal corrosiveness was measured by the mass change before and after extrusion. The smaller the mass change, the smaller the metal corrosiveness.

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 hypophosphate monohydrate as a polymerization catalyst. The mixture was placed in a ribbon blender type reactor, sealed with nitrogen, and heated to 170 ° C. with stirring at a rotation speed of 30 rpm. Then, while keeping the temperature at 170 ° C. and the rotation speed at 30 rpm, 4.98 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as a diamine component using a liquid injection device was added to 2 A reaction product was obtained by adding the mixture continuously (continuous liquid injection method) over 5 hours. The molar ratio of the raw material monomer is TPA: DDA: STA = 48.5: 49.6: 1.9 (the equivalent ratio of the functional groups of the raw material monomer is TPA: DDA: STA = 49.0: 50.0). : 1.0).
Subsequently, the obtained reaction product was polymerized by heating in the same reaction apparatus under a nitrogen stream at 250 ° C. and a rotation speed of 30 rpm for 8 hours to prepare a polyamide powder.
Then, the obtained polyamide powder was formed into strands using a twin-screw kneader, the strands were passed through a water tank to be cooled and solidified, and the strands were 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 Ltd.)
-Polyamide (A-6): Polyamide 46 (TW300 manufactured by DSM)

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

(2) Metal phosphinic acid salt (B)
B-1: Aluminum diethylphosphine (Exolit OP1230 manufactured by Clariant AG)

(3) Hydrazine-based compound (C) having a hindered phenol structure
C-1: N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine (CDA-10 manufactured by ADEKA CORPORATION)

(4) Reinforcing 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 (Micro Ace K-1 manufactured by Japan Talc), average particle size 8 μm

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

(6) Phosphorus-based antioxidant F-1: Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite (Hostanox P-EPQ manufactured by Clariant)

(7) Triazole-based compound G-1: 2-hydroxy-N-1H-1,2,4-triazole-3-yl-benzamide (CDA-1 manufactured by ADEKA CORPORATION)

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 part by mass of metal compound (E-1) A part and 0.3 parts by mass of a phosphorus-based antioxidant (F-1) were dry-blended and weighed using a loss-in-weight continuous quantitative supply device CE-W-1 type (manufactured by Kubota), and the screw diameter was 26 mm. , L / D50 isodirectional twin-screw extruder TEM26SS type (manufactured by Toshiba Machine Co., Ltd.) was supplied to the main supply port and melt-kneaded. On the way, 45 parts by mass of the reinforcing material (D-1) was supplied from the side feeder, and further kneading was performed. After taking it into a strand shape from the die, it was passed through a water tank to be cooled and solidified, and it was cut with a pelletizer to obtain a polyamide resin composition pellet. The barrel temperature of the extruder was set (melting point −5 to + 15 ° C.), screw rotation speed 250 rpm, and discharge rate 25 kg / h.

Examples 2-32 and Comparative Examples Polyamide resin composition pellets were obtained in the same manner as in Example 1 except that the compositions of the polyamide resin compositions were changed as shown in Tables 3-4. The resin composition pellets represented by Comparative Example nC such as Comparative Example 1C have the same composition as the pellets of the resin composition of Example n except that they do not contain the hydrazine-based compound (C) having a hindered phenol structure. Is.

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

Since the resin composition of the example satisfies the requirements of the present invention and contains a hydrazine-based compound (C) having a hindered phenol structure, a comparative example that does not contain the hydrazine-based compound (C) having a hindered phenol structure. Compared with the resin composition of No. 1, the flame retardancy was improved and the metal corrosiveness at high temperature was suppressed.
In Examples 1, 12 to 15, the resin composition was found to have improved 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 the metal salt of phosphinic acid, but was remarkably highly corrosive to metal. The flame retardancy similar 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), in the examples containing the hydrazine-based compound having a hindered phenol structure, the content of the metal phosphinic acid salt can be reduced and the metal corrosiveness can be suppressed. Is now possible.
From the comparison of Examples 1 to 6, the resin compositions 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 have less mold stains. The releasability was excellent. From the comparison between Example 1 and Example 3, the resin composition of Example 1 using the aliphatic monocarboxylic acid as the monocarboxylic acid component was more than the resin composition of Example 3 using the 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 had better mechanical properties.
The resin composition of Example 6 containing an aliphatic polyamide (A-6) having a melting point of 285 ° C. and a high water absorption rate was found to have one or two blisters (blisters) on a test piece in a reflow resistance test. An outbreak was seen. However, the resin compositions of all the other examples containing the semi-aromatic polyamide containing the terephthalic acid component and having a low water absorption rate were excellent in reflow resistance, and the appearance of the test piece was not changed. In the reflow resistance test, a test piece for flame retardancy evaluation was subjected to moisture absorption treatment at 85 ° C. × 85% RH for 168 hours, and then placed in an infrared heating type reflow oven at 150 ° C. for 1 minute. The temperature was raised 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-shaped talc. Was there.
In comparison with Examples 1 and 22 to 30, the resin composition contained a metal compound to suppress metal corrosiveness. The resin compositions of Examples 29 and 30 in which the metal compound contains a metal carbonate and a fatty acid metal salt are flame-retardant as compared with the resin compositions of Examples 1, 27 and 28 containing one kind of metal compound. It has become possible to suppress the deterioration of sex.
In the resin composition of Example 30, since the polyamide contains a semi-aromatic polyamide and an aliphatic polyamide, the fluidity is improved as compared with the resin composition of Example 29 in which the polyamide is only a semi-aromatic polyamide. However, the shear heat generation of the resin was suppressed, the metal corrosiveness could be further suppressed, and despite the inclusion of the aliphatic polyamide, it had reflow resistance.
In the comparison between Examples 1 and 31, the resin composition was found to have improved 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, and the resin compositions of Example 8 have a flame retardancy of V-1, and are more flame-retardant than the resin compositions of other examples. Although it was inferior, the metal corrosiveness was greatly suppressed.

The resin compositions of Comparative Examples 1 and 2 were inferior in flame retardancy because they did not contain or contained a small amount of the metal phosphinic acid salt.
Since the resin composition of Comparative Example 3 contained a large amount of the metal salt of phosphinic acid, it was excellent in flame retardancy, but the metal corrosiveness was remarkably high. 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 corrosiveness was not suppressed. In Comparative Example 7, when the content of the metal phosphinic acid salt was further increased, the strands could not be taken up 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 the 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 also saturated. Was.
Since the resin composition of Comparative Example 9 used a triazole-based compound having a hydrazine structure in the ring but not a hindered phenol structure instead of the hydrazine-based compound having a hindered phenol structure, Example 1 No effect of improving flame retardancy was observed as compared with the resin composition of.

EX: Biaxial kneading extruder D: Die MP: Metal plate R: Flow path of molten resin

Claims (8)

A polyamide resin composition containing a polyamide (A), a metal phosphinic acid salt (B), and a hydrazine-based compound (C) having a hindered phenol structure.
The mass ratio (A / B) of the polyamide (A) to the metal phosphinic acid salt (B) is 60/40 to 95/5.
The content of the hydrazine-based compound (C) having a hindered phenol structure is 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). Polyamide resin composition. The polyamide resin composition according to claim 1, wherein the polyamide (A) has a melting point of 270 to 350 ° C. The first aspect of claim 1, wherein 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 any one of claims 1 to 3, 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 independently represent an alkyl group or a phenyl group having 1 to 16 carbon atoms in a linear or branched chain, respectively. R ³ is a linear or branched chain or branched chain. It represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkyl arylene group. 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 relational expression of 2 × b = n × a.) The claim is characterized in that the reinforcing material (D) is further contained, and the content thereof is 5 to 200 parts by mass with respect to a total of 100 parts by mass of the polyamide (A) and the phosphinic acid metal salt (B). The polyamide resin composition according to any one of 1 to 4. Further, at least one metal compound (E) selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal borate salts, metal tinic acid salts, metal fatty acid salts, hydrotalcites 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 sixth aspect of claim 6, wherein the metal compound (E) contains a metal carbonate and a fatty acid metal salt, and the mass ratio (metal carbonate / fatty acid metal salt) is 90/10 to 30/70. Polyamide resin composition. A molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 7.

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