JPH06184431A - Flame-retardant polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in the suppression of gas generation and heat resistance, useful for electrical parts, part materials, etc., by incorporating a polyamide with a specific organic halogen compound, flame retarding auxiliary, phosphite and filler at specified proportion. CONSTITUTION:This resin composition can be obtained by incorporating (A) 100 pts.wt. of a polyamide such as nylon 66 with (B) 2-80 (pref. 10-70) pts.wt. of an organic halogen compound 50-90 (pref. 55-80) wt.% in halogen content, (C) 0-50 (pref. 1 40) pts.wt. of a flame retarding auxiliary such as antimony oxide, (D) 0.001-20 (pref. 0.01-5) pts.wt. of a phosphite compound of the formula (R1 and R5 are each H, 1-10C alkyl, aryl or aralkyl; R2-R5 are each 1-10C alkyl, aryl or aralkyl) and (E) 0-250 pts.wt. of a filler such as glass fibers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant polyamide resin composition. In particular, the present invention relates to a flame-retardant polyamide resin composition suitably used for parts such as connectors in the electric and electronic fields, electrical parts such as connectors in the automotive field, and other useful parts materials.

In particular, the present invention relates to a flame-retardant polyamide resin composition in which the amount of gas generated at the time of molding, a large amount of deposits on a mold and the flame-retardant performance are improved, and which is excellent in heat aging resistance. .

[0003]

2. Description of the Related Art Polyamide resins have been used in the fields of electric / electronic parts, automobile parts, mechanical parts, etc. due to their good mechanical properties, molding processability and chemical resistance. In particular, in electrical and electronic parts applications, the demand level for flame retardancy has become higher and higher in recent years, and higher flame retardancy than the inherent self-extinguishing properties of polyamide resin is required. Underwriters Laboratory UL -9
Studies have been conducted to improve the flame retardancy level based on the 4 standards.

On the other hand, it is generally known that a flame retardant of a polyamide resin is added with a halogen-based flame retardant. For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (JP-A-48-29846), addition of a brominated flame retardant such as decabromodiphenyl ether (JP-A-47-7134), and bromination. Addition of polystyrene (JP-A-51-47044, JP-A-4-1)
75371), addition of brominated polyphenylene ether (JP-A-54-116054), addition of brominated cross-linked aromatic polymer (JP-A-63-317552, JP-A-56-152863). Addition of brominated styrene-maleic anhydride polymer (JP-A-3-1682)
No. 46) has been used in combination with a flame retardant aid such as antimony oxide.

Further, in recent years, the demand for heat-resistant aging performance has become strict, and in the use of electric and electronic parts,
There is a demand for higher heat-resistant aging performance due to an increase in heat generation due to high-density mounting of LSIs mounted on a laminated board and an increase in engine output in automotive parts applications.

[0006] Up to now, due to the above background, there has been no request for prevention of coloration when a polyamide resin composition containing a halogen-based flame retardant has been heat-aged, so this study has hardly been made. .

As a conventional technique, pentaerythritol diphosphite is added to a composition containing an engineering resin such as a polyamide resin for the purpose of improving a change in color tone due to heat deterioration (Japanese Patent Laid-Open No. 63-25415).
No. 7), an organic cyclic phosphite compound is added to a composition containing the resin for the purpose of preventing the color change of the polyamide resin (JP-A-3-97755), and a biphenylene phosphite is added (JP-A No. 7-75755). No. 4-170430) has been tried, but none of them relates to suppression of color tone change before and after extrusion or molding, and there is no disclosure about a polyamide resin composition containing a halogen-based flame retardant.

As a recent example, a phosphate such as disodium phosphate is added to the polyamide resin containing a halogen-based flame retardant to prevent granulation and coloration (JP-A-3-24).
No. 4664), but in this case, the pellet color tone is brown but the pellet color tone immediately after the granulation shows a bad result even though the granulation property is good.

As a similar example, Japanese Patent Laid-Open No. 969/1992
According to the example of JP-A-70, tetrakis (2,4-di-butylphenyl) -4,4'-biphenylenediphosphite or tris (2,4-di-butylphenyl) phosphite is used as disodium phosphate. However, since the former two types of phosphorus-based stabilizers described in Examples of the publication have poor hydrolysis resistance, they are added to polymers having high water absorption such as polyamide resin. Then, during storage, the phosphite is hydrolyzed, which deteriorates the appearance of the molded product and lowers the heat aging resistance.

Further, the latter is inferior in heat resistance and generates gas at the time of molding, thus contaminating the mold as described in Examples. Regarding a polyamide resin containing a halogen-based flame retardant, JP-A-2-142852 discloses an attempt to suppress decomposition of the flame retardant and improve heat resistance of the composition by adding hydrotalcite. However, since hydrotalcite is an ionic substance, it causes deterioration of electrical performance, which is not preferable.

[0011]

The improvement of flame retardancy can be achieved by increasing the amount of the above-mentioned halogen-based flame retardant and flame retardant aid such as antimony oxide, but these decrease the mechanical strength. There is a problem of inviting.

When a polyamide having a high melting point is used (particularly, when the melting point is as high as 260 ° C. like nylon 66), the processing temperature must be further raised and it contains a flame retardant. Polyamide resin causes mold contamination such as mold corrosion due to gas generation due to unpurified volatile components of flame retardant derived from flame retardant and its decomposition products during melt molding, and adhesion of mold to the mold, resulting in lower productivity. Or, it will be mixed into the molded product as a foreign substance. Further, it has a drawback that the decomposition and deterioration of the polyamide due to the generation of these volatile components are promoted and the appearance of the molded product is deteriorated.

In view of the above circumstances, the inventors of the present invention are excellent in suppressing the amount of gas generated when molding a polyamide resin containing a halogen-based flame retardant, reducing the amount of mold deposits, and the appearance and heat aging resistance of molded products. , And earnestly studied to obtain a flame-retardant polyamide resin composition having improved flame retardancy.

[0014]

Means for Solving the Problems In the present invention, as a result of intensive studies to solve the above problems, a polyamide resin is combined with a specific flame retardant, a flame retardant aid, a phosphite compound and an inorganic reinforcing material. It was found that all the problems can be solved by the above, and arrived at the present invention.

The present invention will be described in detail below. That is, the present invention is: (A) 2 to 80 parts by weight of an organic halogen compound having a halogen content of 50 to 90% by weight, (C) antimony oxide, sodium antimonate, and oxidized to 100 parts by weight of polyamide. At least one flame retardant aid selected from tin, iron oxide, zinc oxide and zinc borate 0 to 50
Parts by weight, (D) phosphite compound having a structure represented by the following chemical formula 3 and / or the following chemical formula 4 0.001
20 parts by weight and

[0016]

[Chemical 3]

(However, R ₁ and R ₆ are hydrogen or a carbon number 1
Alkyl groups, aryl groups and aralkyl groups of 10 and they may be the same or different. Also,
R ₂ , R ₃ , R ₄ and R ₅ are an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and they may be the same or different. )

[0017]

[Chemical 4]

(However, R ₁ is an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group. R ₂ and R ₃
Is hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group,
It is an aralkyl group, and they may be the same or different. R ₄ and R ₅ are an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and they may be the same or different. R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms. )

(E) A flame-retardant polyamide resin composition comprising 0 to 250 parts by weight of a filler. The phosphite compound is bis (2,4,6-
Trialkyl-substituted phenyl) pentaerythritol-di-phosphite, 2,2-alkylenebis (4,6-dialkyl-substituted phenyl) alkyl phosphite, 2,2
-Alkylenebis (4,6-dialkyl-substituted phenyl)
It is also characterized in that it is at least one phosphite compound selected from substituted phenyl phosphites.

The component (A) used in the present invention is a polymer having an amide bond, and it is a polymer obtained by polycondensing an organic diamine and an organic dicarboxylic acid, a polymer obtained by polycondensing an aminocaproic acid, and a lactam. And a polymer obtained by ring-opening.

Examples of organic diamines are 1,4-diaminobutane, 1,6-diaminohexane, 1,7-tetramethylenediamine, 1,8-diaminooctane, 1,
Examples thereof include aliphatic alkylenediamines such as 10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane, and metaxylylenediamine containing an aromatic ring, but are not limited thereto.

Examples of the organic dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. .

Examples of aminocaproic acid include ε-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Examples of lactams include ε-caprolactam and ω-laurolactam,
It is not limited to these. The polyamide used in the present invention may be a homopolymer, a copolymer, or a blend thereof.

The number average molecular weight of polyamide is 5,000 to
About 50,000 is preferable. As a concrete example of the above,
Nylon 66, Nylon 6, Nylon 46, Nylon 6
6/6, nylon 66 / 6T, nylon 66 / 6I, nylon 6T / 6I, nylon 66 / 6T / 6I, nylon 66 / 6T / 612, nylon MXD6, and the like, and one or various polyamides can be used.

The component (A) is not limited to these, but in particular, nylon 66 or 50% by weight thereof is used.
The copolymer or polymer blend containing the above has a melting point,
It is preferable as a part material for electric / electronic fields and automobile fields, which has a high heat distortion temperature and requires solder resistance.

The halogen content of component (B) is 5
It is 0 to 90% by weight, preferably 55 to 80% by weight. If the halogen content is less than the predetermined amount, the flame retardant effect is not sufficient, and if the halogen content is more than the predetermined amount, the elimination of halogen may be promoted under high temperature conditions during kneading, which may lead to an accelerated release.

The component (B) is used in an amount of 2 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the component (A).

When the amount is less than a predetermined amount, the flame retardant effect is not sufficient, and when the amount is more than the predetermined amount, a corrosive gas is generated due to the volatile oligomer contained in the component during kneading or molding and its decomposition component. May occur, which may lead to a decrease in productivity such as the adherence of a pollutant to the molding die, the deterioration of the appearance color tone of the molded product, and the inclusion of foreign matter.

As the component (B) used in the present invention,
Chlorine-based flame retardants and bromine-based flame retardants are generally used. Examples of chlorine-based flame retardants include dodecachloropentacyclooctadeca-7,15-diene and the like, and specifically, there is Dechlorane Plus 25 <registered trademark> manufactured by Oxydental Chemical.

Examples of brominated flame retardants include brominated polystyrene, brominated crosslinked aromatic polymers, brominated styrene maleic anhydride polymers, brominated polyphenylene ethers, brominated epoxy resins and brominated phenoxy resins. Not limited. Specific examples of the above include Pyrocheck 68PB <registered trademark> and Pyrocheck L manufactured by Ferro.
M <registered trademark>, Great Lakes PDBS-80
<Registered Trademark>, PDBS-10 <Registered Trademark>, EBR-370FK <Registered Trademark> manufactured by Manac Co., PO64P <Registered Trademark> manufactured by Great Lakes, F24 manufactured by Maksim
00 <registered trademark> and the like.

As the component (B), a bromine-based flame retardant is preferable from the viewpoints of flame retardancy and thermal decomposition resistance, and above all, heat resistance,
From the viewpoint of non-bleed-out property, brominated polystyrene, brominated polyphenylene ether, and brominated crosslinked aromatic polymer are preferable, and brominated polystyrene and brominated polyphenylene ether are particularly preferable.

The component (C) can be used as a flame retardant aid for the component (B), and antimony oxides such as diantimony trioxide, diantimony tetroxide and diantimony pentoxide;
Tin oxides such as sodium antimonate, tin monoxide, and tin dioxide; ferric oxides such as ferric oxide and γ-iron oxide; boric acid represented by zinc oxide, 2ZnO · 3B ₂ O · 3.5H ₂ O, etc. Examples include zinc.

Specific examples of the component (C) antimony oxide include Patox C <registered trademark>, Patox M <registered trademark>, Apox S <registered trademark>, manufactured by Sumitomo Metal Mining Co., Ltd. Antimony oxide KU and FS <
Registered trademark>, Piroguard AN-7 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
00, AN-800 and AN-900 <registered trademark> and the like.

Examples of sodium antimonate include San Epoch NA-1075 <registered trademark> manufactured by Nissan Chemical Industries, Ltd., Sodium Antimonate-S manufactured by Nippon Seiko Co., Ltd., and the like. Specific examples of zinc oxide include ZAT manufactured by Sakai Chemical Industry Co., Ltd.
EX special number <registered trademark>, Toho Zinc Co., Ltd. silver mine A <registered trademark> and the like.

Specific examples of zinc borate include FIREBRAKE 290 <registered trademark> (Zinc borate ZB2335) manufactured by Borax, USA. Component (C) is
It may be used in the range of 0 to 50 parts by weight, preferably 1 to 40 parts by weight, relative to 100 parts by weight of the component (A), and may be used alone or in combination of two or more.

This is because if the amount is more than the predetermined amount, the mechanical properties of the polyamide resin according to the present invention will be deteriorated. Further, in order to improve the flame retardancy effect, the flame retardant aid preferably has an average particle size of 0.01 to 10 μm. Flame retardant aids except zinc borate have an average particle size of 0.1 to 2
The thickness is preferably μm, and is 0.1 to 1.2 μm.

If the average particle size is smaller than the predetermined average particle size, the handling becomes difficult and the productivity is lowered. If the average particle size is larger than the predetermined average particle size, the flame retardancy is deteriorated. In this case, in order to exhibit flame retardancy equivalent to that when a predetermined average particle size is used, a large amount of flame retardant component (B) must be used, resulting in mold corrosion and mold deposits. The result is an increase.

In particular, it is preferable to use the above-mentioned antimony trioxide having a small average particle size, and other flame retardant aids can also be used. The component (D) is a phosphite compound having a structure represented by the following chemical formula 5 and / or the chemical formula 6 below.

[0039]

[Chemical 5]

(However, R ₁ and R ₆ are hydrogen or 1 carbon atom.
Alkyl groups, aryl groups and aralkyl groups of 10 and they may be the same or different. Also,
R ₂ , R ₃ , R ₄ and R ₅ are an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and they may be the same or different. )

[0041]

[Chemical 6]

(However, R ₁ is an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group. R ₂ and R ₃
Is hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group,
It is an aralkyl group, and they may be the same or different. R ₄ and R ₅ are an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and they may be the same or different. R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms. )

As a concrete example of the above, for example, a screw (2,
6-di-t-butylphenyl) pentaerythritol-
Diphosphite, bis (2,6-di-t-butyl-4-
Methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol-diphosphite,

Bis (2,6-di-t-butyl-4-isopropylphenyl) pentaerythritol-di-phosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol- Diphosphite, bis (2,6-di-t-butyl-4-sec-butylphenyl) pentaerythritol-diphosphite,

Bis (2,6-di-t-butyl-4-t-
In addition to pentaerythritol type phosphite compounds such as octylphenyl) pentaerythritol-diphosphite and bis (2,6-di-t-butyl-4-t-nonylphenyl) pentaerythritol-diphosphite The pentaerythritol type diphosphite described in JP-A-63-254157 and the like can be mentioned.

Further, as the above-mentioned examples, 2,2-alkylenebis (4,6-dialkylphenyl) alkyl phosphite, 2,2-alkylenebis (4,6-dialkylphenyl) alkyl-substituted phenylphosphite and 2,2-alkylenebis (4,6-dialkylphenyl) alkyl-substituted phenylphosphite 2-alkylenebis (4,6-dialkylphenyl) phenylphosphite and the like.

The alkylene group referred to here is ethylidene,
Examples include substituted methylene such as isopropylene and methylidene. The alkyl group of the 4,6-di-alkyl group referred to herein preferably has 1 to 9 carbon atoms, and the alkyl group of the alkylphosphite has 1 to 30 carbon atoms.
Is preferred.

Specific examples of the above include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) stearylphosphite. Fight, 2,2-methylenebis (4,6-di-t-butylphenyl) -2,6
-Di-t-butyl-4-methylphenyl phosphite and the like, and organic cyclic phosphite compounds described in JP-A-3-97755.

The component (D) can be used in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the component (A). It is preferably 0.01 to 5 parts by weight. Ingredient (D)
When the amount used is less than the predetermined amount, the volatile halogen-containing compound derived from the decomposition product such as the oligomer component of the flame retardant and hydrogen halide deteriorates the polyamide resin, and the heat aging resistance of the resin composition is deteriorated. And the generation of these volatile halogen-containing compounds result in mold corrosion and also reduce the flame retardant effect.

On the other hand, when the amount is larger than the predetermined amount, the flame retardant effect is synergistically improved with the use of the flame retardant (C), but the mechanical properties are deteriorated.

As the component (E), glass fiber, carbon fiber, aromatic aramid fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica , Calcium carbonate, glass beads, glass flakes, clay, wollastonite, titanium oxide, hydrotalcite, and other fibrous, powdery, or plate-like inorganic substances. These fillers may be used alone or in combination of two or more.

In particular, glass fiber is preferably used in the above filler. The type of glass fiber is not particularly limited as long as it is used for general resin reinforcement, and short fiber type or long fiber type chopped strand, milled fiber or the like can be selected and used. In addition, the glass fiber is ethylene / vinyl acetate copolymer, urethane type,
It may be coated or bundled with an acrylic resin, an epoxy resin, a polyester resin or the like, or may be treated with a silane or titanate coupling agent or another surface treatment agent.

For the purpose of preventing a change in color tone, it is preferable to use an antioxidant together with the component (D) since a synergistic effect is exhibited. As the above-mentioned antioxidant, the following compounds are typified by the hindered phenol compounds shown below.

For example, triethylene glycol-
Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate],

2,4-bis- (n-octylthio) -6
-(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3-3,5-di-t-butyl-4-hydroxyphenyl) propionate ],

Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-t)
-Butyl-hydroxy-hydrocinmanide), 3,5
-Di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester,

1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-)
Hydroxybenzyl) -isocyanurate and the like.

Specific products include, for example, Irganox <registered trademark> 245, 25 manufactured by Ciba Geigy.
9,565,1010,1035,1076,108
1, 1098, 1222, 1330, 3114 and the like.

The resin composition of the present invention contains, in addition to the above-mentioned antioxidants, a light stabilizer, an ultraviolet absorber, a lubricant, a release agent, a dye or a pigment, etc., within a range not impairing the object of the present invention. Common additives such as colorants, plasticizers, antistatic agents, and other thermoplastic resins can be added to impart predetermined characteristics.

The method for producing the resin composition of the present invention is not particularly limited. For example, polyamide resin, specific flame retardant,
In addition to specific flame retardant aids and fillers, compatibilizers if necessary,
Using a known melt-kneader such as a single-screw or multi-screw extruder, a kneader, a mixing roll, or a Banbury mixer, a mixture of a phosphorus compound, a metal compound, and other additives such as the above-mentioned additives is used in an amount of 200 to 400. A method of melt-kneading at a temperature of ° C can be mentioned. In particular, it can be melt-kneaded using an extruder.

Further, after melt-kneading a mixture consisting of some components of the resin composition of the present invention, a mixture containing the remaining components may be blended and molded before molding, or one of the resin compositions of the present invention may be blended. The present resin composition may be finally prepared after preparing a masterbatch made of a polyamide resin containing some components. In the melt-kneading of the resin composition of the present invention or the molding after blending, the addition method, order, etc. of the components of the resin composition of the present invention are not limited.

[0062]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The properties described in Examples and Comparative Examples were evaluated by the following methods. (Evaluation methods)

Color tone: Pellets were prepared at 80 ° C. under a nitrogen stream until the water content in the pellets was 0.05% or less, the cylinder temperature of the molding machine was 280 ° C., the mold temperature was 8
Injection molding was carried out under the condition of 0 ° C. The molded product is ASTM
Using a test piece according to -D638, the color tone of the surface of the test piece after injection molding was visually determined.

Flame Retardance: US UNDER WRITE
UL-9 defined by RS LABORATORIES
It measured according to the standard of 4. It was carried out on a test piece having a thickness of 1/32 inch. Gas generation amount (TGA characteristic): Using a thermogravimetric measuring device TGA-50 manufactured by Shimadzu Corporation, 30 mg of pellets prepared by was collected, and the pellet was heated at 25 ° C to 2 under nitrogen flow.
The temperature was raised to 290 ° C. at 0 ° C./minute, and the decrease in thermogravimetric weight when 90 minutes had elapsed from the start of temperature increase was shown in percentage. Heat aging resistance: 180 ° C for the test piece prepared in
Heat aging treatment in an oven for 10 days at
The color tone change of the test piece was visually determined.

Mold adhesion: 30 seconds / using a cylinder (diameter 50 mm, height 50 mm, bottom thickness 3 mm, top thickness 1.5 mm) for injection molding in which the gate enters the center of the bottom of the cylinder at a right angle 2,000 shots of continuous molding were performed in a cycle. After molding, take out the cylindrical insert,
The state of deposits on the surface was visually evaluated.

Average particle size: 5 samples in a beaker
0 mg was collected, 100 ml of water was poured, the sample was uniformly dispersed, and then ultrasonicated for 5 minutes. For the measurement, a centrifugal sedimentation type particle size distribution measuring device (SA-CP3 manufactured by Shimadzu Corporation) was used.

Further, in the following Examples and Comparative Examples,
As the polyamide, Yuki halogen compound, flame retardant aid, phosphite compound, filler and antioxidant, the following compounds or products were used.

(Polyamide) Nylon 66 Asahi Kasei Kogyo KK Leona <registered trademark> 1300 (organic halogen compound) Polydibromophenylene ether: Great Lakes PO64P <registered trademark> (bromine content 62%)

(Flame Retardant Auxiliary Agent) Antimony trioxide: Nihon Seiko Co., Ltd. Seito Patox M <registered trademark> average particle diameter 0.6 μm Nippon Seiko Co., Ltd. Patox C <registered trademark> average particle diameter 3.1 μm Sumitomo Mining company antimony oxide KU <registered trademark> average particle size 0.9 μm Sumitomo Metal Mining Company antimony oxide K <registered trademark> average particle size 2.1 μm Daiichi Kogyo Seiyaku Co., Ltd. pyrogallol AN-700 <registered trademark> average particle Diameter 0.7 μm

(Phosphite compound) Bis (2,6-di-t-butylphenyl) pentaerythritol-di-phosphite: Adeka Stab PEP-36 <registered trademark> 2,2 manufactured by Asahi Denka Co., Ltd. -Methylenebis (4,6-di-t-butylphenyl) octyl phosphite: Adeka Stab HP-10 <registered trademark> manufactured by Asahi Denka Co., Ltd.

(Filler) Glass fiber (GF): ECS03T-289 <registered trademark> manufactured by Nippon Electric Glass Co., Ltd. (average length 3 mm, average diameter 13 μm) (antioxidant) N, N′-hexamethylenebis (3 , 5-di-t-butyl-hydroxy-hydroxynmanide): Ciba Geigy Irganox 1098 <registered trademark>

(Examples 1 to 9) In the formulations shown in Tables 1 and 2, required amounts of raw materials were blended in a tumbler type blender, and the resulting mixture was melt-kneaded by an extruder set to a cylinder temperature of 280 ° C. to obtain strands. A water-cooled iron was cut with a cutter to obtain pellets having a water content of 0.05% or less.

As the extruder, PCM45 (rotating in the same direction) manufactured by Ikegai Tekko KK having a screw diameter of 45 mmφ was used. Among the raw materials, the glass fiber was of the side-feed type. The composition pellet thus obtained was molded by an injection molding machine (N-70BII manufactured by Nippon Steel Co., Ltd.) to prepare a molded product. Regarding the evaluation, according to the above-mentioned method, the color tone of the molded article, the heat resistant aging color tone, the gas generation amount, the flame retardance (UL-94), and the die attachment were carried out. The results are shown in Tables 3-4.

Comparative Examples 1 to 4 Extrusion, granulation, pellet preparation and molding were carried out in the same manner as in Example 1 with the formulations shown in Tables 1 and 2. The results are shown in Tables 3-4.

[0075]

[Table 1]

[0076]

[Table 2]

A) Irgaphos 168 manufactured by Ciba Geigy
<Registered trademark>: tris (2,4-di-t-butylphenyl) phosphite b) Asahi Denka Co., Ltd. ADEKA STAB PEP-24
G <registered trademark>: Bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite c) Sand Stub P-EPQ <registered trademark>: Tetrakis (2,4-di-t-) Butylphenyl)-
4,4′-biphenylenediphosphite d) manufactured by Ciba Geigy Irganox 1098 <registered trademark>: N, N′-hexamethylenebis (3,5-di-)
t-butyl-hydroxy-hydroshikinamanide),

The results are shown in Tables 3-4.

[Table 3]

[0079]

[Table 4]

A) Color tone determination: ⊚; pale gray white, ○
Mark: Light brown white, × mark; Brown b) Mold adhesion determination: ◎ mark: 10% or less of the external surface, ○ mark: 20% or less of the external surface, Δ mark: Less than 50% of the external surface, × mark 50% or more of the outer surface

[0081]

In each of the examples, the amount of gas generated is improved by 30% or more as compared with the comparative example, and the heat aging resistance is also good. Also, with respect to flame retardancy, all of the examples are good, and particularly the examples 1 to 6 are more effective than the comparative examples. Furthermore, regarding die attachment,
The result is better than any of the comparative examples.

As shown in the above Examples and Comparative Examples, the resin composition in which the specific phosphite compound is blended with the composition comprising the halogen-based flame retardant and the polyamide resin is remarkably reduced in the gas generated during molding, Greatly improved mold adhesion, as well as excellent flame resistance and heat aging resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08K 5/524 KLB 7242-4J C09K 21/14 8318-4H

Claims (2)

[Claims] 1. To 100 parts by weight of (A) polyamide,
(B) 2 to 80 parts by weight of an organic halogen compound having a halogen content of 50 to 90% by weight, (C) antimony oxide,
0 to 50 parts by weight of at least one flame retardant aid selected from sodium antimonate, tin oxide, iron oxide, zinc oxide, and zinc borate, (D) Formula 1 and / or Formula 2 below. 0.001 to 20 parts by weight of a phosphite compound having a structure represented by: (However, R ₁ and R ₆ are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and they may be the same or different. Further, R ₂ , R ₃ , R ₄ and R ₅ is an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and they may be the same or different.) (However, R ₁ is an alkyl group having 1 to 30 carbon atoms, an aryl group, or an aralkyl group. R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and R ₄ and R ₅ are an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms, and they may be the same or different, and R ₆ is hydrogen or 1 to 10 carbon atoms. The flame-retardant polyamide resin composition comprises (E) 0 to 250 parts by weight of a filler. 2. The phosphite compound is bis (2,4,6-trialkyl-substituted phenyl) pentaerythritol-di-phosphite, 2,2-alkylenebis (4,6-dialkyl-substituted phenyl). The flame-retardant property according to claim 1, which is at least one phosphite compound selected from alkyl phosphite and 2,2-alkylenebis (4,6-dialkyl-substituted phenyl) -substituted phenyl phosphite. Polyamide resin composition.