JP2000053860A - Flame-retardant resin composition and molded product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a molded product having highly excellent flame retardancy, a low specific gravity, and excellent mechanical properties, electrical characteristics (tracking resistance), and wet-heat resistance by mixing a polyamide resin with a polycarbonate resin, and red phosphorus having a specified conductivity in a specified ratio. SOLUTION: This composition comprises 100 pts.wt. polyamide resin, 0.1-50 pts.wt. polycarbonate resin, 0-50 pts.wt. polyethylene terephthalate and 0.1-30 pts.wt. red phosphorus having a conductivity of 0.1-1,000 μS/cm. The conductivity of the red phosphorus is the conductivity of the aqueous extract obtained by adding 5 g of red phosphorus to 100 ml of deionized water, extraction-treating the red phosphorus at 121 deg.C for 100 hr and diluting the filtrate left after the filtration of red phosphorus to 250 ml. The red phosphorus used is desirably one coated with a thermosetting resin, especially, a thermoplastic phenolic resin. It is desirable that the composition additionally contains 5-140 pts.wt. per 100 pts.wt. polyamide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition using a non-halogen flame retardant. More specifically, the present invention relates to a flame-retardant resin composition having excellent flame retardancy and mechanical properties and suitable for automobile parts, electric / electronic parts, and mechanical parts.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyamide resins, polyester resins, polycarbonate resins, and polyphenylene oxide resins make use of their excellent characteristics.
As an injection molding material, it is being used in a wide range of fields such as mechanical parts, electric and electronic parts, and automobile parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method tends to generate a large amount of smoke during combustion. Further, the resin composition containing the halogen-based flame retardant has a problem that the electric characteristics are deteriorated.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

Heretofore, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it has been widely known to add a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method for flame retarding a polyamide resin without using such a hydrated metal compound, addition of red phosphorus is disclosed in JP-A-60-168775 and JP-A-61-219706. JP-A-63-89567, JP-A-1-129061, JP-A-2-16
No. 9666, JP-A-3-197553, JP-A-6-145504, JP-A-6-263983 and the like. Japanese Patent Application Laid-Open No. 5-320486.
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a method for improving flame retardancy and electric properties by adding red phosphorus. However, any resin composition exhibits excellent flame retardancy in a thick (1/16 ") molded article, but has a thin (1/32") molded article required with recent resin material thinning. There was a problem that sufficient flame retardancy could not be obtained. Japanese Patent Laid-Open No. 5-32
There has been a problem that the flame retardancy of the resin composition obtained by the method described in Japanese Patent No. 0486 is insufficient, and the effect of improving the electrical properties is not sufficient.

Further, the resin composition obtained by any of the methods has a problem that the mechanical properties are deteriorated and the flame retardant bleeds out during dry heat treatment.

[0008]

That is, the present invention relates to a thin molded article (1/32 ") using a non-halogen flame retardant.
It is an object of the present invention to obtain a resin composition which imparts high flame retardancy, has excellent mechanical properties and electrical properties (tracking resistance), has a low specific gravity, and has low contact contamination on the metal surface. .

More specifically, the thin-walled molded article has excellent flame retardancy, mechanical properties, and electrical properties, has a low specific gravity, and has excellent resistance to contact contamination due to wet heat treatment.
The present invention relates to a flame-retardant resin composition suitable for electric / electronic parts and automobile parts.

[0010]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result, it has been found that the blending of a specific amount of a polycarbonate resin, a polyethylene terephthalate resin, and red phosphorus with a polyamide resin provides a very high level of performance. It has been found that a resin material having a low specific gravity and excellent mechanical properties, electrical properties (tracking resistance), and moisture and heat resistance while maintaining flame retardancy can be obtained, and the present invention has been achieved.

That is, the present invention relates to (B) (B-1) 0.1 to 50 parts by weight of a polycarbonate resin and (B-2) 0 to 50 parts by weight of a polyethylene terephthalate resin per 100 parts by weight of a polyamide resin. And (C) 0.1 to 30 red phosphorus having a conductivity of 0.1 to 1000 μS / cm.
A flame-retardant resin composition containing 100 parts by weight of pure phosphorus in 5 g of red phosphorus and 100 ml of pure water at 121 ° C.
Extraction is performed for a period of time, and the filtrate after red phosphorus filtration is set to have a conductivity of extracted water diluted to 250 mL. The above flame-retardant resin composition, wherein the red phosphorus (C) is red phosphorus coated with a thermosetting resin, and the polyamide resin (A) further contains 5 to 140 parts by weight of a filler with respect to 100 parts by weight. The above-mentioned flame-retardant resin composition, the above-mentioned flame-retardant resin composition whose filler is glass fiber, a polyamide resin (A) component,
In the component (B), (B-1) a polycarbonate resin, (B
-2) polyethylene terephthalate resin, and (C)
When compounding red phosphorus, a part of component (A) or part or all of component (B) and (C) red phosphorus are once melt-kneaded to produce a red phosphorus high concentration composition (D), Producing the above-mentioned flame-retardant resin composition by melt-kneading the remaining components (A), (B) and the red phosphorus-rich composition (D) with a twin-screw extruder. A method for producing a resin composition, and the present invention further provides a molded article comprising the flame-retardant resin composition, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part, wherein the molded article is a connector, a coil bobbin, or a relay. Alternatively, the molded article which is a switch, and the present invention further comprises (B-2) 0 to 200 parts by weight of a polyethylene terephthalate resin and (C) electrical conductivity of 0.1 to 100 parts by weight of a polycarbonate resin (B-1). At 1000 μS / cm That the red phosphorus 30-20
It is a flame retardant for polyamide resin containing 0 parts by weight.
(However, the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, performing an extraction treatment at 121 ° C. for 100 hours, and diluting the solution after filtration of the red phosphorus to 250 mL to extract water.)

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below. Examples of the polyamide resin (A) used in the present invention include polyamides mainly containing amino acids, lactams or diamines and dicarboxylic acids, and these may be any of aliphatic polyamides and semi-aromatic polyamides. These polyamide resins (A) are usually produced by a known method, and specific examples of raw materials that can be used include, for example, lactam compounds such as ε-caprolactam and ω-laurolactam, 6-aminocaproic acid, 12-aminododecanoic acid, Aminocarboxylic acid compounds such as 11-aminoundecanoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid,
Dicarboxylic acid compounds such as oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,6-hexamethylenediamine, trimethyl-1,6-hexamethylenediamine, 4,4 ′
-Diaminodicyclohexylenemethane, 4,4'-diaminodicyclohexylenepropane, and diamine compounds such as 2-methylpentamethylenediamine. Among them, ε-caprolactam, ω-laurolactam, 12-aminododecanoic acid, 11-aminoundecanoic acid, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, 1,6-hexamethylenediamine, or Mixtures of two or more are preferred, and more preferably ε-caprolactam, ω-
One or a mixture of two or more selected from laurolactam, 12-aminododecanoic acid, 11-aminoundecanoic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and 1,6-hexamethylenediamine.

The polyamide resins useful in the present invention include polyamide 6 (polycaproamide), polyamide 46 (polytetramethylene adipamide) and polyamide 6
6 (polyhexamethylene adipamide), polyamide 61
0 (polyhexamethylene sebacamide), polyamide 61
2 (polyhexamethylene dodecamide), polyamide 11
(Polyundecaneamide), polyamide 12 (polydodecaneamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide MXD6 (polyxylene adipamide), nylon HTN (poly (2 -Methylpentamethylene terephthalamide)), nylon 9T
(Polynonamethylene terephthalamide) and copolymers thereof, and these can be used alone or in combination of two or more. Among them, aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 11, and polyamide 12, polyamide 6T / 66 (copolymer of hexamethylene terephthalamide (6T) and hexamethylene adipamide (66)), nylon 6T / 12 Semi-aromatic polyamides such as (copolymer of hexamethylene terephthalamide (6T) and polyamide 12) and copolymers thereof can be preferably used, and polyamide 6, polyamide 66 and copolymers thereof are particularly preferred. is there.

In the component (B) used in the present invention, the polycarbonate resin (B-1) is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. Alternatively, the copolycarbonate resin has a viscosity average molecular weight of 10,000 to 1
000000 range. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis ( 4-hydroxy-3,
5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis ( 4-Hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture.

The polycarbonate resin (B-1) of the present invention
Is added in an amount of 0.1 to 50 parts by weight, preferably 1 to 45 parts by weight, based on 100 parts by weight of the polyamide resin (A).
More preferably, it is 5 to 40 parts by weight.

In the present invention, (B-1)
Although the effects of the present invention are exhibited only by the polycarbonate resin alone, by blending the polyethylene terephthalate resin (B-2), not only high flame retardancy but also mechanical properties, heat resistance, and high temperature and high humidity conditions are obtained. Bleed-out and low contact contamination during processing are improved. (B-2)
The addition amount of the polyethylene terephthalate resin is 0 to 50 parts by weight based on 100 parts by weight of the polyamide resin (A).
Preferably 0.1-45 parts by weight, more preferably 1-4.
0 parts by weight.

In the component (B), the mixing ratio of the (B-2) polyethylene terephthalate resin is determined from the viewpoint of flame retardancy, fluidity and tracking resistance of the obtained resin composition.
The amount is preferably from 0 to 98% by weight, more preferably from 5 to 90% by weight, particularly preferably from 1 to 98% by weight, based on the total amount of the component (B).
0 to 80% by weight.

Next, the red phosphorus (C) used in the present invention will be described.

The red phosphorus (C) used in the present invention is unstable as it is, and gradually dissolves in water,
Since it has a property of gradually reacting with water, a material which has been treated to prevent this is preferably used. As such a method of treating red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and the red phosphorus is formed without forming a crushed surface having high reactivity with water or oxygen on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, a method of coating red phosphorus with paraffin or wax to suppress contact with moisture Method, stabilization by mixing with ε-caprolactam or trioxane, phenol-based, melamine-based, epoxy-based red phosphorus,
A method of stabilizing by coating with a thermosetting resin such as an unsaturated polyester system, red phosphorus is copper, nickel,
A method in which a metal phosphorus compound such as silver, iron, aluminum and titanium is treated with an aqueous solution to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus.Aluminum hydroxide, magnesium hydroxide, titanium hydroxide, water Examples include a method of coating with zinc oxide or the like, a method of stabilizing the surface of red phosphorus by electroless plating with iron, cobalt, nickel, manganese, tin, or the like, and a method of combining them. A method of pulverizing red phosphorus without forming a crushed surface on the surface of red phosphorus without pulverization of red phosphorus, coating red phosphorus with thermosetting resin such as phenolic, melamine, epoxy, unsaturated polyester type By coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. It is particularly preferable to use a method in which red phosphorus is finely divided without forming a crushed surface on the surface of red phosphorus, and heat curing of red phosphorus such as a phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based. This is a method of stabilizing by coating with a conductive resin. Among these thermosetting resins, phenol-based thermosetting resin, red phosphorus coated with epoxy-based thermosetting resin can be preferably used from the viewpoint of moisture resistance, and phenol-based thermosetting resin is particularly preferable. Red phosphorus coated with resin.

The average particle size of red phosphorus before being blended with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, moisture and heat resistance, and chemical and physical deterioration of red phosphorus due to grinding during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. The particle size distribution measuring apparatus includes a wet method and a dry method, and any of them may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The average particle diameter of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more is difficult. Since the flammability, mechanical properties, wet heat resistance, and recyclability tend to be remarkably reduced, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoints of flame retardancy, mechanical properties, wet heat resistance and recyclability. It is. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the particle diameter contained in red phosphorus is 75 μm.
The above-mentioned red phosphorus content can be measured by classification using a 75 μm mesh. That is, red phosphorus 100
g (g) when g is classified with a 75 μm mesh
Thus, the content of red phosphorus having a particle size of 75 μm or more is A / 100 ×
It can be calculated from 100 (%).

The conductivity of the red phosphorus (B) used in the present invention when it is extracted in hot water (where the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, for example, in an autoclave to obtain 121%). Extraction at 100 ° C. for 100 hours, and diluting the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water) is the moisture resistance, mechanical strength, tracking resistance, and recyclability of the obtained molded product. 0.1 ~
1000 μS / cm, preferably 0.1 to 800
μS / cm, more preferably 0.1 to 500 μS / c
m.

Examples of such preferred commercial products of red phosphorus include "NOVA EXCEL 140" and "NOVA EXCEL F5" manufactured by Rin Kagaku Kogyo KK and equivalents thereof.

In the present invention, the amount of red phosphorus (C) added is
0.1 to 30 parts by weight, preferably 1 to 30 parts by weight, more preferably 2-2 to 100 parts by weight of the polyamide resin.
7 parts by weight, more preferably 5 to 25 parts by weight. If the amount is too small, the flame retardancy tends to be poor. If too much, the mechanical properties will be inferior,
The flame retardancy also worsens.

[0027] The flame-retardant resin composition of the present invention can significantly improve the strength, rigidity, heat resistance and the like by further adding a filler.

Such a filler may be fibrous or non-fibrous, such as granular, and specific examples thereof include:
Glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastenite,
Examples include glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.

The amount of these additives is determined by the amount of polyamide resin (A) 1
The amount is preferably from 5 to 140 parts by weight, particularly preferably from 5 to 100 parts by weight, per 100 parts by weight.

The flame retardant resin composition of the present invention can further improve the stability, strength, heat resistance and the like during extrusion and molding by adding a metal oxide as a stabilizer for red phosphorus. Specific examples of such a metal oxide include:
Cadmium oxide, zinc oxide, cuprous oxide, cupric oxide,
Ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and titanium oxide, among which cadmium oxide, cuprous oxide,
Cupric oxide, titanium oxide is preferred, especially cuprous oxide,
Cupric oxide and titanium oxide are preferred.

The addition amount of the metal oxide is preferably 0.1 to 100 parts by weight of the polyamide resin (A) from the viewpoint of mechanical properties and moldability.
It is preferably from 0.01 to 20 parts by weight, particularly preferably from 0.1 to 20 parts by weight.
10 parts by weight.

If the flame-retardant resin composition of the present invention is further added with a fluorine-based resin and / or a silicone-based compound, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The amount of the fluororesin to be added is generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polyamide resin (A) from the viewpoint of mechanical properties and moldability.
Parts by weight, more preferably 0.2 to 3 parts by weight.

The flame-retardant resin composition of the present invention can further suppress the drop (drip) of droplets during combustion by adding a silicone compound.

The above-mentioned silicone compound is a silicone resin and / or silicone oil.

The silicone resin used in the present invention is:
Chemically bonded siloxane units selected from units represented by the following general formulas (1) to (4) and mixtures thereof (where R is a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, A polyorganosiloxane comprising a group selected from a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or an allyl group, and preferably a methyl group and / or a phenyl group. Although a resin having a viscosity of centipoise is preferable, the viscosity is not limited to the above silicone resin.

[0037]

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The silicone oil used in the present invention is represented by the following general formula (5) (where,
R represents an alkyl group or a phenyl group, particularly preferably a methyl group and / or a phenyl group.
n is an integer of 1 or more. ). The silicone oil used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited to the above silicone oil.

[0039]

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In the present invention, a silicone resin and / or silicone oil can be used as the silicone-based compound. However, flame retardancy, heat resistance, bleed-out resistance, contact contamination resistance, and deterioration of electrical properties after wet heat treatment. In view of the above, a silicone resin is preferable.

The amount of the silicone compound added depends on the mechanical properties,
From the viewpoint of moldability, it is usually 0.01 to 10 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the polyamide resin (A).
It is 1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

It is also possible to use a fluorine-based resin and a silicone-based compound in combination. In this case, the total addition amount of the fluorine-based resin and the silicone-based compound is preferably 100% by weight of the polyamide resin (A) in terms of mechanical properties and moldability. Parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.2 to 3 parts by weight.
Parts by weight.

It has been found that when the flame retardant resin composition of the present invention is further used in combination with a hindered phenol-based oxidation stabilizer, extremely good mechanical properties are maintained even when exposed to high temperatures for a long period of time. As such a stabilizer, 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], 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, 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, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based oxidation stabilizer can be added as required, and the amount of the hindered phenol-based oxidation stabilizer added at this time is usually the polyamide resin (A ) 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 0.5 part by weight, per 100 parts by weight.

The flame retardant resin composition of the present invention can be imparted with higher flame retardancy by further adding a salt of a triazine compound and cyanuric acid or isocyanuric acid. The salt of triazine compound and cyanuric acid or isocyanuric acid of the present invention is an adduct of cyanuric acid or isocyanuric acid and triazine compound,
Usually 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio)
Is an adduct having the following composition: Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

Examples of the triazine-based compound include compounds represented by the following general formula (6).

[0047]

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In the general formula (6), R ¹ , R ² ,
R ³ and R ⁴ are the same or different, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
ONH ₂ . Here, the aryl group has 6 to 6 carbon atoms.
Preferred are those having 15 carbon atoms, those having 1 to 10 carbon atoms as alkyl groups, those having 7 to 16 carbon atoms as aralkyl groups, and those having 4 to 15 carbon atoms as cycloalkyl groups. Also, R ⁵ -NR ¹ in the above formula is R ² or -NR ³ R ⁴
Or a group independently of these, or a hydrogen, an aryl group,
Alkyl group, aralkyl group, cycloalkyl group, -NH
_2, or a group selected from -CONH _2, where the aryl groups those having from 6 to 15 carbon atoms, the alkyl group as having 1 to 10 carbon atoms, aralkyl group of 7 to 16 carbon atoms And cycloalkyl groups having 4 to 15 carbon atoms are preferred.

Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrogen, phenyl, p-toluyl, α-naphthyl,
β-naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group , A cycloheptyl group, a 2-methyl-1-pentyl group, a 4-methyl-1-cyclohexyl group, an amide group and the like, among which hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group And an amide group is preferred.

Specific examples of R ⁵ include an amino group, an amide group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a mono (hydroxymethyl) amino group, and a di (hydroxymethyl) amino group. , Mono (methoxymethyl) amino group, di (methoxymethyl)
Amino group, phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Of the salts of the compound represented by the general formula (6) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine,
Amide-4,6-diamino-1,3,5-triazine,
Mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine salts are preferred, especially melamine, benzoguanamine,
Acetoguanamine salts are preferred.

The salt of the triazine compound and the cyanuric acid or isocyanuric acid is prepared by mixing a mixture of the triazine compound and the cyanuric acid or isocyanuric acid with a water slurry and mixing them well to form fine particles of both salts. Thereafter, this slurry is a powder obtained by filtering and drying, and is different from a mere mixture. The salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain.

The average particle size of the salt is 100 to 0.01 μm in view of the flame retardancy, mechanical strength and surface properties of the molded product.
And more preferably 80 to 10 μm.
If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The amount of the salt used is as follows.
Usually, 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 00 parts by weight.
30 parts by weight.

The flame-retardant resin composition and the molded article of the present invention, by blending an elastomer, not only reduce the flame retardancy but also improve the impact properties,
Bleed-out during wet heat treatment can be significantly suppressed.

The elastomer is not particularly limited as long as it has a glass transition temperature of room temperature or lower.
For example, polyolefin polymers such as polypropylene and polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, styrene resin, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer (ABS resin) and other polyolefin copolymers such as styrene resins, elastomers such as polyester polyether elastomers and polyester polyester elastomers, and mixtures of two or more of these synthetic resins. Also ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer And an ethylene / propylene-g-maleic anhydride copolymer can be preferably used.

The amount of the elastomer is 0.1 to 100 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the polyamide resin contained in the finally obtained flame-retardant resin composition and molded article. ~ 80 parts by weight, more preferably 1
７０70 parts by weight.

Further, phosphorus- and sulfur-based antioxidants other than hindered phenols, heat stabilizers, ultraviolet absorbers and the like can be used in the flame-retardant resin composition of the present invention as long as the object of the present invention is not impaired. One or more ordinary additives such as a lubricant, a releasing agent, and a coloring agent including a dye or a pigment can be added.

The flame-retardant resin composition of the present invention is produced by a generally known method. For example, in the polyamide resin (A) and the component (B), (B-1) a polycarbonate resin, (B
-2) Polyethylene terephthalate resin, red phosphorus (C)
And other necessary additives are preliminarily mixed or supplied to an extruder or the like, and are sufficiently melt-kneaded. However, from the viewpoint of handling properties and productivity, polyamide resins ( Part of A) or (B)
In the components, (B-1) part or all of the polycarbonate resin, or (B-2) part or all of the polyethylene terephthalate resin and red phosphorus (C) are once melt-kneaded and actually flame-retarded resin composition A resin composition (D) having a higher red phosphorus concentration than the amount of red phosphorus to be blended with the polyamide resin is prepared, and the remaining polyamide resin (A) or (B) contains (B-
1) Polycarbonate resin, (B-2) resin composition having high red phosphorus concentration in polyethylene terephthalate resin (D)
And other optional additives can be prepared by melt-kneading.

Alternatively, part of the polyamide resin (A) or part or all of the component (B), (B-1) part or all of the polycarbonate resin, or (B-2) part or all of the polyethylene terephthalate resin, and red phosphorus (C) A resin composition having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame retardant resin composition by melt-kneading (C) and other optional additives. And the remaining (A) polyamide resin (A) or (B)
In the components, (B-1) a polycarbonate resin, (B-2)
It is prepared by melt-kneading the polyethylene terephthalate resin and additives other than the optional additives added at the stage of the resin composition (D) having a high red phosphorus concentration.

At the stage of producing the resin composition (D) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the flame-retardant resin composition as described above, it can be used arbitrarily. When the additives are compounded, it is preferable that these optional additives can be mixed with red phosphorus in advance.

Among the additives which can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide, is added, the titanium oxide produces a red phosphorus-rich product (D). It is preferable to mix at the stage,
Further, if red phosphorus and titanium oxide are previously mixed using a mechanical mixing device such as a Henschel mixer, the stability of red phosphorus, the dispersibility of red phosphorus, and the non-coloring property of the obtained resin composition are improved. be able to.

The compounding amount of red phosphorus in the high-red-phosphorus-concentration product (D) is determined in terms of production of the high-concentration red-phosphorus product, dispersibility of red phosphorus,
From the viewpoint of flame retardancy, mechanical properties and moldability of the finally obtained resin composition, (A) polyamide resin, (B-
1) at least one kind of resin 100 selected from 1) polycarbonate resin and (B-2) polyethylene terephthalate resin
The amount is preferably from 30 to 300 parts by weight, particularly preferably from 35 to 200 parts by weight, based on parts by weight.

As the red phosphorus high concentration product (D), (1)
(A) Red phosphorus high concentration product consisting only of polyamide resin,
(2) (B-1) Red phosphorus high concentration product consisting only of polyethylene terephthalate resin, and (3) (B-2) Red phosphorus high concentration product (D) consisting only of polycarbonate resin exhibit the present effect. However, when (B-1) a high-concentration red phosphorus product composed of a polycarbonate resin, or (B-1) a combination of a polycarbonate resin and (B-2) a polyethylene terephthalate resin, the resin in the high-concentration red phosphorus product (D) is And red phosphorus compatibility are further improved, red phosphorus dispersibility,
The flame retardancy, mechanical properties and tracking resistance of the finally obtained resin composition are improved.

In this case, the red phosphorus high concentration product (D) is (B)
-1) For 100 parts by weight of the polycarbonate resin,
(B-2) Polyethylene terephthalate resin 0 to 200
Parts by weight, (C) 30 to 300 parts by weight of red phosphorus having a conductivity of 0.1 to 1000 μS / cm.

The (B-) of such a high red phosphorus concentration product (D)
2) The blending amount of the polyethylene terephthalate resin is determined in terms of manufacturability in the production of a high-concentration product of red phosphorus, dispersibility of red phosphorus,
From the viewpoint of flame retardancy, mechanical properties, moldability, and tracking resistance of the finally obtained resin composition, (B-1) 0 to 200 parts by weight based on 100 parts by weight of the polycarbonate resin.
The weight is preferably from 0 to 180 parts by weight, more preferably from 1 to 150 parts by weight.

The resin composition having a high red phosphorus concentration (D)
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. The polybutylene terephthalate resin and the polyethylene terephthalate resin to be mixed with the component (D) are preferably in the form of pellets, but are not limited thereto, and may be in the form of chips, powders, or a mixture of chips and powders. Is also good. Further, it is preferable that the form, size, and shape of the component (D) and the polyamide resin, polycarbonate resin, and polyethylene terephthalate resin to be blended with the component (D) are substantially the same or similar to each other because they can be uniformly mixed. In producing the resin composition, for example, a single-screw extruder equipped with a “unimelt” type screw, a twin-screw extruder, a tri-screw extruder, and a kneader-type kneader can be used.

The resin composition (D) having a high red phosphorus concentration of the present invention imparts flame retardancy to the polyamide resin, and therefore can be used as a flame retardant for polyamide resins.

The flame-retardant resin composition and the molded article thus obtained can be usually molded by a known method, and molded articles such as injection molding, extrusion molding and compression molding, and molded articles of all shapes such as sheets and films. It can be.
Among them, it is particularly suitable for use in injection molded products. It is also suitable for molded products with complicated shapes such as molded products with welds and hinges and insert molded products, and thin molded products.
It is suitable for various mechanical mechanism parts, electric and electronic parts or automobile parts.

For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage , FDD chassis, HDD parts, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio parts・ Sound equipment parts such as laser discs and compact discs, lighting parts,
Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Stern bearings, underwater bearings, and other various bearings, motor parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, cameras,
Optical equipment represented by watches, precision machinery-related parts, alternator terminals, alternator connectors,
IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump,
Engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air Flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor-related parts, dust distributor, starter switch, starter relay, transmission wiring harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetics Valve coil, fuse connector, horn terminal, electrical component insulation board, step It is useful for various applications such as rotor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases. It can be suitably used for connectors, coil bobbins, relays, and switches as parts that make use of flammability and impact characteristics, moisture and heat resistance, low contact contamination, and light weight.

[0071]

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Mechanical Characteristics A molded by injection molding at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd.
The tensile yield strength was measured according to STM D-638.

(2) Impact characteristics A molded by injection molding at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd.
Izod impact strength of 1/4 inch (notched) thickness was measured according to STM D-256.

(3) Deflection temperature under load Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., A was injection molded at a molding temperature of 280 ° C. and a mold temperature of 80 ° C.
The deflection temperature under load at a load of 1.82 MPa was measured according to STM D-648.

(4) Flame Retardancy A test piece for evaluating flame retardancy obtained by injection molding using an IS55EPN injection molding machine made by Toshiba Machine at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. UL94
The flame retardancy was evaluated according to the evaluation criteria set forth in. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB. The sum of the burning times of the five samples was used as an index of flame retardancy.

(5) Moisture / heat resistance (contact contamination) A copper plate of 1 mm thick and 1 cm square is covered with 100 g of resin composition pellets in a 500 ml Erlenmeyer flask, sealed, sealed at a temperature of 121 ° C. and a humidity of 100% RH. The discolored state of the copper plate after the treatment for 24 hours was observed. ：: no discoloration, Δ: slightly discolored, ×: considerably discolored, the contact contamination was evaluated in three stages.

(6) Specific gravity Measured according to ASTM D-792. Reference Example 1 Production of polyamide resin <A-1> Amilan CM3001, which is polyamide 66
(Manufactured by Toray Industries, Inc.) (abbreviated as N66 in the table).

<A-2> Amilan C which is polyamide 6
M1010 (manufactured by Toray Industries, Inc.) was used (abbreviated as N6 in the table).

<A-3> The following polyamide copolymer was produced as the polyamide 66 copolymer.

A mixed aqueous solution (solid raw material concentration: 60% by weight) of 30 mol% of hexamethylene diammonium terephthalate (6T salt) and 70 mol% of hexamethylene diammonium adipate (AH salt) is charged into a pressure polymerization vessel and stirred. After raising the temperature and reacting for 1.5 hours at a water vapor pressure of 19 kg / cm ² , the pressure was gradually released over about 2 hours, and further reacted for about 30 minutes under a normal pressure nitrogen stream to obtain a relative viscosity of 2.63 (1% Sulfuric acid (98%)
The middle polyamide 6T / 66 was obtained. 278 ° C.

<A-4> The following polyamide copolymer was produced as the polyamide 66 copolymer.

An aqueous mixed solution of 62 mol% of hexamethylene diammonium terephthalate (6T salt), 26 mol% of hexamethylene diammonium isoterephthalate (61 salt) and 12 mol% of hexamethylene diammonium adipate (AH salt) (solid raw material concentration: 60%) % By weight) into a pressure polymerization vessel, and the temperature was increased with stirring, and 1% at a steam pressure of 35 kg / cm2.
After reacting for an hour, the pressure was gradually released over about 2 hours to obtain a polyamide. Then, after drying this polyamide, melt polymerization at a cylinder temperature of 330 ° C. using a twin-screw extruder,
A polyamide 6T / 6I / 66 having a relative viscosity of 2.3 (in 1% sulfuric acid (98%)) was obtained. Melting point 320 [deg.] C.

Reference Example 2 Production of Red Phosphorus Concentrated Product (D) <Production of (D-1): PET // Red Phosphorus Concentrated Product (Conductivity)
200 μm S / cm)> polyethylene terephthalate (hereinafter abbreviated as PET) 10 having an intrinsic viscosity of 0.65 (25 ° C., phenol / tetrachloroethane 1: 1 mixed solvent)
Red phosphorus (“NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd .: average particle size 29.7 μm), 100 g of pure water was added to 5 g of red phosphorus, and 1 part at 121 ° C. in an autoclave.
After extraction for 00 hours, the back solution obtained by filtering red phosphorus
diluted to mL and conductivity meter (Personal SC manufactured by Yokogawa Electric Corporation)
200 μm S /
), and a resin temperature of 280 was mixed using a coaxially rotating twin-screw extruder (TEX-30, manufactured by Nippon Seiko Co., Ltd.) having a screw diameter of 30 mm and L / D = 45.5 while performing a nitrogen flow. The mixture was melt-extruded at a temperature of 0 ° C. to produce a PET red phosphorus-rich product (D-1). After drying the obtained red phosphorus high concentration product at 110 ° C, injection molding (cylinder temperature 280)
C. and a mold temperature of 80 ° C.) to prepare a combustion test piece, and the resistance to moist heat contamination was evaluated. Wet heat contact contamination: ○.

<Production of (D-2): PC // high concentration of red phosphorus (conductivity: 200 μm S / cm)> 100 parts by weight of polycarbonate resin “Iupilon” S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation) The procedure was the same as (D-1) except that 100 parts by weight of red phosphorus (Rinno Kagaku Kogyo's “NOVA EXCEL 140”) was used. Wet heat contact contamination: ○.

<Production of (D-3): PET // PC // Red phosphorus high concentration product (conductivity: 200 μm S / cm)> PET resin 1
100 parts by weight of polycarbonate resin "Iupilon" S3000 (manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) and 200 parts by weight of red phosphorus ("NOVA EXCEL" 140 manufactured by Rin Kagaku Kogyo Co., Ltd.) were mixed. While performing flow, screw diameter 30mm, L
The resin was melt-extruded at a resin temperature of 280 ° C. using a coaxial rotary twin screw extruder (/D=45.5, manufactured by Nippon Seiko Co., Ltd.) to produce a red phosphorus-rich product (D-3). Using the red phosphorus high concentration product, the moisture and heat contact contamination resistance was evaluated in the same manner as in Reference Example 1 above. Wet heat contact contamination: ○.

<Production of (D-4): Polyamide 66 // Red phosphorus high concentration product (conductivity: 200 μm S / cm)> Amilan CM3001 (manufactured by Toray Industries, Inc.) (hereinafter abbreviated as N66) 100 which is polyamide 66 100 parts by weight of red phosphorus (“NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd.) is mixed with the parts by weight, and the screw diameter is 30 m while performing a nitrogen flow.
Melt extrusion at a resin temperature of 280 ° C using a coaxial rotary twin screw extruder (manufactured by Nippon Seiko Co., Ltd., TEX-30) with m / L / D = 45.5, N66 high concentration of red phosphorus (D-4) Was manufactured. Wet heat contact contamination: △.

<Production of (D-5): PET // PC // Red phosphorus high concentration product (conductivity: 1200 μm S / cm)> PET resin 1
100 parts by weight of polycarbonate resin "Iupilon" S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation) and 100 parts by weight of "Nova Red" 120 (manufactured by Rin Kagaku Kogyo Co., Ltd.)
m, conductivity 1200 μS / cm, red phosphorus content 15% or more having a particle size of 75 μm or more) (D-
Performed in the same manner as in 2). Wet heat contact contamination: △.

From the production of the high-concentration red phosphorus product shown in Reference Example 2 above, D-1 to D-
In No. 4, a red phosphorus high concentration product excellent in moisture and heat contact contamination resistance can be obtained.

The high-concentration red phosphorus product comprising red phosphorus having a specific conductivity produced in Reference Example 2 and D-1 to D-4 was mixed with the resin composition in a small amount to obtain flame retardancy,
It has been found that a flame-retardant resin composition having not only low specific gravity and resistance to moisture and heat contact contamination but also excellent tracking resistance, heat resistance and mechanical properties can be obtained. Hereinafter, the present effect will be described with reference to examples and comparative examples, but the present effect is not limited to these examples.

Examples 1 to 5 and Comparative Examples 1 to 3
C, a high-concentration red phosphorus product produced in Reference Example, glass fiber, and other additives were mixed, and a screw diameter of 30 mm, L
/D45.5 co-rotating twin screw extruder (Nippon Steel Corporation,
TEX-30: The screw uses two screws of 3.5 mm with each other with 2 threads, and L / D = 4.
A screw element consisting of 10 kneading discs inclined at 5 degrees is provided in reverse order, and a reverse full flight element is provided.
And melt extruded at a resin temperature of 280 ° C. After drying the obtained pellets, injection molding (cylinder temperature 280 ° C,
ASTM D-638, D-25 depending on mold temperature 80 ° C)
6, tensile test specimens, impact test specimens specified in D-648, tensile test specimens, impact test specimens specified in load deflection test specimens, and test specimens for evaluating flame retardancy based on UL94 (1
/ 32 ″) was prepared. In Example 4, the same procedure was followed as in Example 4 except that melt extrusion was carried out using the above-mentioned apparatus while using a nitrogen flow without using a high-concentration red phosphorus product.

Each sample was measured for flame retardancy, tensile strength, impact strength, specific gravity, moisture and heat bleed-out, and moisture and heat contact contamination. Table 1 shows the results.

The glass fiber reinforced system was blended so that the glass fiber weight% in the resin composition was 30% by weight based on 100% by weight of the whole resin composition.

In the table, GF represents glass fiber (“CS3PE941S” manufactured by Nitto Boseki Co., Ltd.).

[0094]

[Table 1]

From the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 3, a specific amount of PC resin or PET was added to polyamide 66.
By blending resin and red phosphorus with specific conductivity, it has specifically high flame retardancy, and excellent mechanical properties and heat resistance,
It can be seen that a flame-retardant resin composition excellent in moisture and heat contact contamination can be obtained.

Comparative Example 1 shows that only polyamide 66 and red phosphorus having a specific conductivity cannot provide flame retardancy, are inferior in mechanical properties and tracking resistance, have high specific gravity, and have low contact contamination. .

When the amount of PC is larger than that in Comparative Example 2, although the flame retardancy rank is V-0, a tendency that the burning time is prolonged is recognized. Although the specific gravity is reduced, mechanical properties, tracking resistance, and heat resistance are remarkably reduced, and moisture-heat contact contamination resistance is reduced.

Even when the specific amounts of the PC resin and the PET resin are used as in Comparative Example 3, when red phosphorus having high conductivity is used, not only the tracking resistance but also the contact contamination when wet and heated is remarkably reduced.

From the comparison between Example 2 and Example 4, Example 2 using the high-concentration red phosphorus product had the same flame retardancy rank V-.
Even at 0, the combustion time is short, and the mechanical properties tend to be slightly superior, and it can be seen that the moisture and heat contact contamination resistance is particularly improved.

From the comparison of Examples 1 to 3, it was found that the case of using a high concentration of red phosphorus composed of PC (Example 1), the case of using a high concentration of red phosphorus composed of PET (Example 2), and that of PC When a high-concentration product of red phosphorus made of PET is used (Example 3), the latter has a short burning time and tends to have slightly better mechanical properties.

Examples 7 to 9 <A-2> to <A-2> described in Reference Examples as polyamide resins
A-4>, PC, a high-concentration red phosphorus product produced in Reference Example, glass fiber, and other additives were mixed at the compounding ratio shown in Table 2, and a screw diameter of 30 mm, L / D45.
5 twin-screw extruder (TEX-3, manufactured by Nippon Steel Corporation)
0: The screw uses two screws of 3.5 mm mutually meshing with two threads, and screw elements consisting of 10 kneading disks inclined at 45 degrees with L / D = 4 are provided in reverse order. , And a screw shape with a strong kneading force provided with a reverse full flight element).
Melt extruded at 0 ° C to 350 ° C. (In the case of <A-2>: 280 ° C., in the case of <A-3>: 3
20 ° C, <A-4>: 350 ° C) After drying the obtained pellets, ASTM D-638, D-
Tensile test specimen, impact test specimen specified in 256, D-648, tensile test specimen, impact test specimen specified in load deflection test specimen, and test specimen for evaluating flame retardancy based on UL94 (1/32 ") The cylinder temperature / mold temperature was <A-2>: 28
0 ° C / 80 ° C <A-3>: 320 ° C / 80 ° C, <A-4>: 350 ° C / 80 ° C.

[0102] The flame retardancy, tensile strength, impact strength, specific gravity, and moisture and heat contact contamination of each sample were measured. Table 2 shows the results
Shown in

[0103]

[Table 2]

According to Examples 7 to 9, regardless of N66, even for other polyamide resins, a specific amount of PC resin or PET resin and a specific amount of red phosphorus having a specific conductivity are blended to obtain a specific high flame retardancy. It can be seen that a flame-retardant resin composition having excellent mechanical properties and heat resistance, and having excellent resistance to moisture and heat contact contamination can be obtained.

[0105]

The flame-retardant resin composition of the present invention has not only high flame retardancy but also excellent mechanical properties, heat resistance, low specific gravity, and excellent tracking resistance. Since it is excellent in moisture-heat contact contamination resistance, it is suitable for mechanical mechanism parts, electric / electronic parts or automobile parts. In particular, connectors, coil bobbins, relays, and switch parts that have a contact surface with metal and are used under severe conditions are required to have high flame retardancy, mechanical properties, heat resistance, and low specific gravity. Flame-retardant resin compositions are suitable for these uses.

Claims (9)

[Claims] 1. A polycarbonate resin (B) (B-1) 0.1 to 50 parts by weight based on 100 parts by weight of a polyamide resin (A).
Parts by weight, (B-2) 0 to 50 parts by weight of a polyethylene terephthalate resin, and (C) a conductivity of 0.1 to 1000 µS / cm
A flame-retardant resin composition containing 0.1 to 30 parts by weight of red phosphorus. (However, conductivity is 5 g of red phosphorus and 100 mL of pure water.
, And the mixture is extracted at 121 ° C. for 100 hours, and the filtrate after red phosphorus filtration is diluted to 250 mL to obtain the conductivity of the extracted water. ) 2. The flame-retardant resin composition according to claim 1, wherein the red phosphorus (C) is red phosphorus coated with a thermosetting resin. 3. The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of a filler based on 100 parts by weight of the polyamide resin (A). 4. The flame-retardant resin composition according to claim 3, wherein the filler is glass fiber. 5. The polyamide resin (A) and the component (B), wherein (B-1) a polycarbonate resin, (B-2) a polyethylene terephthalate resin, and (C) red phosphorus are blended with the component (A). Or part or all of the component (B) and (C) red phosphorus are once melt-kneaded to produce a red phosphorus high concentration composition (D), and the remaining components (A) and (B) A flame-retardant resin composition characterized by producing the flame-retardant resin composition according to any one of claims 1 to 4 by melt-kneading the red phosphorus-rich composition (D) with a twin-screw extruder. Method of manufacturing a product. 6. A molded article comprising the flame-retardant resin composition according to claim 1. 7. The molded article according to claim 6, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. 8. The molded article according to claim 6, wherein the molded article is a connector, a coil bobbin, a relay or a switch. 9. (B-1) 0 to 200 parts by weight of a polyethylene terephthalate resin and (C) a conductivity of 0.1 to 10 parts by weight per 100 parts by weight of a polycarbonate resin.
A flame retardant for polyamide resin containing 30 to 200 parts by weight of red phosphorus of 00 μS / cm. (However, the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, performing an extraction treatment at 121 ° C. for 100 hours, and diluting the solution after filtering the red phosphorus to 250 mL to extract water.)