JPH08239574A - Fire retardant resin composition - Google Patents

Abstract

PURPOSE: To obtain a fire retardant resin composition excellent in heat resistance, impact resistance and heat stability during molding and greatly improved in dripping phenomena during burning by using a polybromostyrene having both a number average molecular weight and a molecular weight distribution in specific ranges. CONSTITUTION: This flame retardant resin composition comprises (A) 50-96.9wt.% nylon 4, 6, (B) 3-45wt.% polybromostyrene obtained by polymerizing bromostyrene and having 1×10<4> to 9×10<4> number average molecular weight (Mn) and <=5 Mw/Mn (Mw is a weight average molecular weight) and (C) 0.1-5wt.% dripping protecting agent (e.g. ethylene-glycidyl dimethacrylate copolymer, etc.). Preferably the resin composition can contain 1-200 pts.wt. inorganic filler (e.g. glass fiber, etc.) based on 100 pts.wt. of the sum total of the components A, B and C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is flame retardant having excellent heat resistance, impact resistance and thermal stability at the time of molding, and the dripping phenomenon (flame drop dropping phenomenon) at the time of combustion is greatly improved. Resin composition.

2. Description of the Related Art Polytetramethylene adipamide resin (hereinafter referred to as nylon 4,6) obtained from diaminobutane and adipic acid has excellent mechanical properties such as strength, impact resistance, abrasion resistance, heat resistance and It has high chemical resistance and good moldability, so it is used in various applications such as automobile parts, electrical parts, and general mechanical parts. Nylon is generally a nonflammable material due to its amide group nitrogen due to its chemical structure, and falls into the self-extinguishing category when tested by ASTM D635. However, recently, for the purpose of improving the safety of products used in general households, such as household appliances, electric devices, building materials, and automobile parts, there is a strong demand for flame retardancy, and strict regulations on flame retardancy. It has become to. For this reason, in each country, regulatory measures are taken according to national circumstances, and test methods are being established. In the United States, it is particularly strict, and under the Underwriters Laboratory (hereinafter abbreviated as UL) standard, detailed test methods are determined along with heat resistance, which contributes to the improvement of safety of electrical equipment and the like. With respect to the flame retardancy of synthetic resin compositions used for electric devices, etc., it is V-0 in the combustion test according to the UL-94 test method.
Often required to pass the standard. UL-9
In the 4 test methods, the burning time after flame contact is specified, but at the same time, it is also specified that flame particles that ignite cotton under 12 inches (305 mm) are not dropped. Clarification and prevention measures are strongly desired. Examples of the method of making the resin flame-retardant include flame-retarding by modifying the resin itself, mixing of a non-flammable substance, coating with a non-flammable substance and a flame-retardant substance, addition of a flame retardant, nylon 4, As the flame retarding method of No. 6, as in many other synthetic resins, a method of adding a flame retardant, specifically, a method of blending an organic halogen compound is known. Generally, in the combustion process of resin, heating, melting, deterioration / decomposition,
Although vaporization / diffusion, ignition, and combustion are continued, elucidation of combustion phenomena and elucidation of flame retardation mechanism are not always sufficient because the way of manifestation of phenomena differs depending on individual polymer materials, especially dripping during combustion. There is a strong demand for measures to prevent the phenomenon (flaming drop phenomenon), especially nylon 4,6
In the case of, the melt viscosity was particularly low, which was a big problem. Furthermore, in the case of nylon 4 and 6, due to its high processing temperature, the excellent performance of nylon 4 and 6 cannot be sufficiently maintained with conventional organic halogen compounds, resulting in heat resistance, impact resistance, and thermal stability. Was required to be improved. That is, in the conventional organic halogen compound, nylon 4,
As a flame retardant of No. 6, nylon 4,6 is insufficient in terms of performance maintenance, heat resistance, impact resistance, and thermal stability, and at the same time,
As a nylon 4,6 resin composition, it was necessary to prevent the dripping phenomenon during combustion.

The present invention has been made against the background of the above-mentioned problems of the prior art. By blending a specific flame retardant, heat resistance, impact resistance and heat It is an object of the present invention to provide a flame-retardant resin composition which is stable and has a flame-retardant property, in particular, the dripping phenomenon at the time of combustion is greatly improved by the addition of a dripping inhibitor.

[0002]

The present invention is obtained by polymerizing 50 to 96.9% by weight of (a) nylon 4,6 and (b) brominated styrene monomer, and has a number average molecular weight (Mn )
Is 1 × 10 ^{4 to} 9 × 10 ⁴ , and the weight average molecular weight (M
w) / polybrominated styrene having a number average molecular weight Mn ratio of 5 or less is contained in an amount of 3 to 45% by weight, and (c) an anti-dripping agent is included in an amount of 0.1 to 5% by weight. Flame retardant resin composition, (a) 50 to 96.9% by weight of nylon 4,6, (b) Brominated styrene monomer
Obtained by polymerizing and having a number average molecular weight (Mn) of 1 × 1.
0 is a ⁴ to 9 × 10 ^4, weight average molecular weight (Mw) / number average molecular weight ratio of Mn is 5 or less is polybrominated styrene 3-40 wt%, (c) a dripping inhibitor 0.1 ~
5% by weight, and (d) inorganic fillers (a), (b),
A flame-retardant resin composition comprising 1 to 200 parts by weight relative to 100 parts by weight of the total amount of (c).

Component (a) nylon 4 used in the present invention,
6 is polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid, and contains a copolyamide having a polytetramethylene adipamide unit as a main constituent. Further, another polyamide may be contained as a mixed component within a range not impairing the properties of nylons 4 and 6. The copolymerization component is not particularly limited, and a known amide-forming component can be used. Typical examples of the copolymerization component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminoundecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, and hexamethylene. Diamine,
Undecamethylenediamine, dodecamethylenediamine,
2,2,4- / 2,4,4-Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4- Bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,
5,5-Trimethylcyclohexane, bis (3-methyl-4)
-Aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, diamines such as 2,2-bis (aminoprosyl) piperazine and aminoethylpiperazine, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diamine Acid, terephthalic acid, isophthalic acid, 2
-Chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, dicarboxylic acid such as diglycolic acid, and the like, and Other polyamides used as a mixed component may include those composed of these components. Further, the method for producing the nylons 4 and 6 used in the present invention is arbitrary. For example, JP-A-56-149430,
JP-A-56-149431, JP-A-58-830
No. 29 and JP-A No. 61-43631, that is, first, a prepolymer having a small number of cyclic end groups is produced under specific conditions, and then solid polymerized in a steam atmosphere to obtain a high polymer. There is a method of preparing the viscous nylons 4 and 6, or a method of obtaining it by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone.
The degree of polymerization of nylon 4 and 6 is not particularly limited,
Nylon 4,6 having a relative viscosity at 25 ° C. and 96% sulfuric acid at 1 g / dl of preferably 1.5 to 6 and more preferably 2 to 5 is preferably used. The blending amount of the component (a) nylon 4,6 resin in the present invention is 50.
To 96.9% by weight, preferably 60 to 95% by weight, more preferably 62 to 94% by weight, particularly preferably 65 to 65% by weight.
It is 93% by weight. When the content of the component (a) is less than 50% by weight, the excellent performance and processability of the component (a) are impaired, and when the content of the component (a) exceeds 96.9% by weight, ( Since the blending amount of the component b) is too small, the flame retardancy is poor.

The polybrominated styrene which is the component (b) of the present invention is obtained by polymerizing a brominated styrene monomer such as monobrominated styrene, dibrominated styrene and tribrominated styrene. On the other hand, in the case of brominated polystyrene after brominating a polymer such as polystyrene, it is unavoidable that not only benzene nucleus but also hydrogen in the main chain is replaced by bromine during bromination. At a high temperature such as during processing, that part becomes unstable, and there is a problem that deterioration and decomposition are promoted. On the other hand, polybrominated polystyrene is excellent in that it is stable even at high temperatures because hydrogen in the main chain is not replaced with bromine. The polybrominated polystyrene is preferably a polybrominated styrene having a dibrominated styrene unit content of 50% by weight or more, and more preferably 60% by weight or more. Polybrominated polystyrene is
When the brominated styrene monomer is polymerized, a copolymerizable monomer such as an aromatic vinyl such as styrene, a vinyl cyanide such as acrylonitrile, a vinyl ester compound such as a methacrylic acid ester such as MMA is copolymerized. Good. The bromine content in the polybrominated styrene is preferably 40-75.
%, More preferably 45 to 73% by weight, particularly preferably 50 to 70% by weight. In addition, the number average molecular weight of polybrominated styrene (M
n) is 1 × 10 ^{4 to} 9 × 10 ⁴ , preferably 1 × 10 ^4.
To 7 × 10 ⁴ , more preferably 1 × 10 ^{4 to} 5 × 1
0 ⁴ , particularly preferably 1 × 10 ⁴ to 4 × 10 ⁴ . On the other hand, the weight average molecular weight (Mw) / Mn is 5 or less, preferably 4 or less, and more preferably 1.1 to 3.5. When polybrominated styrene having a number average molecular weight (Mn) and Mw / Mn out of the above ranges is used, at least one of thermal stability, flame retardancy, and impact resistance is the object of the present invention. Can not reach, in other words, thermal stability,
The flame retardancy and impact resistance are all unattainable, and the object of the present invention cannot be achieved. The present invention uses nylon 4,6 as a polyamide resin, and is obtained by polymerizing a brominated styrene monomer as a flame retardant, and has a number average molecular weight of
It is achieved by using polybrominated styrene having Mw / Mn in the above range. A post-bromination type brominated polystyrene obtained by post-brominating polystyrene as a flame retardant cannot achieve the object of the present invention even if the number average molecular weight and Mw / Mn are within the above ranges. The number average molecular weight (Mn) and the weight average molecular weight (M
w) is gel permeation chromatography (G
PC), using tetrahydrofuran (THF) as a solvent to dissolve the flame retardant at a concentration of 1 mg / ml, and measuring at a flow rate of 1.0 ml / min and a temperature of 36 to 40 ° C. to obtain a polystyrene-equivalent number average. The molecular weight (Mn) and weight average molecular weight (Mw) can be obtained. The blending amount of the component (b) polybrominated styrene of the present invention is 3 to 45.
%, Preferably 3.5-40% by weight, more preferably 4-37% by weight, particularly preferably 5-35% by weight. If the blending amount of the component (b) is less than 3% by weight, flame retardancy is poor, and if the blending amount of the component (b) exceeds 45% by weight, excellent performance and processability of the component (a) are impaired.

As the anti-dripping agent of the component (c) of the present invention, a polymer having a specific functional group can be preferably used. Examples of the polymer containing a specific functional group, a functional group-containing olefin polymer, a functional group-containing vinyl polymer,
Alternatively, a polymer having a functional group itself may be used. Examples of the olefin polymer modified with the functional group include polyethylene, polypropylene, polybutylene, ethylene-propylene copolymer, ethylene-butylene copolymer and the like. Further, as the vinyl polymer, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-ethylene-butene copolymer, acrylonitrile-ethylene-propylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer Examples thereof include polymers. Of these, preferred are polyethylene, polypropylene, polybutylene, ethylene-propylene copolymer, styrene-butadiene copolymer, styrene-ethylene-butene copolymer,
It is an acrylonitrile-butadiene-styrene copolymer. Examples of the functional group used in the component (c) of the present invention include at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group. Particularly, a carboxyl group, an acid anhydride group, Epoxy groups are preferred. The functional group-containing olefin polymer or functional group-containing vinyl polymer of the present invention comprises an olefin compound unit or a vinyl compound unit and at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group. It is a binary or multi-component copolymer mainly composed of an unsaturated compound unit. Representative examples of the olefin in the above copolymer include ethylene, propylene, butadiene, butene, pentene, hexene, heptene, methylbutene, methylpentene, and the like, among which ethylene, propylene, and butadiene are preferable. Further, typical examples of the vinyl compound in the above copolymer include styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like, and among these, styrene and acrylonitrile are preferable. Acrylic acid as a representative example of the carboxyl group-containing unsaturated compound in the copolymer,
There are methacrylic acid, maleic acid, etc., typical examples of the acid anhydride group-containing unsaturated compound are maleic anhydride, itaconic anhydride, etc., and vinyl oxazoline is a typical example of the oxazoline group-containing unsaturated compound. As typical examples of the epoxy group-containing unsaturated compound, glycidyl methacrylate and allyl glycidyl ether.
There are tells. Further, with respect to the above copolymer, for example, containing a vinyl compound in the main chain, or by graft polymerization as a side chain also enhances the heat resistance of the functional group-containing polymer used in the present invention, It has the effect of further improving the compatibility with other components in the composition and is preferable for the purpose of the present invention. The amount of the component (c) anti-dripping agent of the present invention is 0.1 to 10% by weight, preferably 0.2 to 7% by weight, more preferably 0.3 to 5% by weight, and particularly preferably 0.1. 4 to 4. If the blending amount of the component (c) is less than 0.1% by weight, the effect as the anti-dripping agent is not recognized, and if the blending amount of the component (c) exceeds 10% by weight, the rigidity decreases.

The flame-retardant resin composition of the present invention also includes the above-mentioned components (a), (b) and (c) further containing an inorganic filler as the component (d). (D)
By using the components, a flame-retardant resin composition having further improved rigidity and dimensional stability can be obtained. The component (d) is various inorganic fillers having fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like shapes.
Glass fiber, asbestos fiber, carbon fiber, graphite fiber, calcium carbonate, talc, catalbot, wollastonite, silica, alumina, silica alumina, diatomaceous earth, clay, calcined clay, kaolin, mica (fine mica), granular glass, Glass flakes, glass balloons (hollow glass), gypsum, red iron oxide, metal fibers, titanium dioxide, potassium titanate whiskers, magnesium oxide, calcium silicate, asbestos, sodium aluminate, calcium aluminate, aluminum, aluminum oxide , Aluminum hydroxide, copper, stainless steel, zinc oxide, metal whiskers and the like. For the purpose of the present invention, glass fiber, carbon fiber, kaolin, mica, and talc are preferable, and glass fiber, kaolin, mica, and talc are particularly preferable because of their economical efficiency. It may be surface-treated as long as it does not impair the moldability and physical properties of the present invention, and among them, those subjected to surface treatment represented by aminosilane treatment, acrylsilane treatment, vinyl treatment and the like are preferable. . The addition amount of the inorganic filler in the present invention is the component (a) of the present invention,
1 to 100 parts by weight of the total amount of the components (b) and (c)
To 200 parts by weight, preferably 2 to 160 parts by weight,
More preferably 3 to 120 parts by weight, particularly preferably 5 parts by weight.
~ 100 parts by weight. When the amount of the inorganic filler added is less than 1 part by weight, the purpose of adding the component (d) cannot be achieved, while
If it exceeds 0 parts by weight, workability, particularly extrusion moldability and injection moldability deteriorates, which is not preferable.

If necessary, a flame retardant aid may be added to the flame retardant resin composition of the present invention in order to further enhance the flame retardancy. Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, antimony compounds such as triphenylantimony, phosphoric acid ester, and the like. Among them, preferred are antimony trioxide and antimony pentoxide. . The amount of flame retardant aid added is
It is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and particularly preferably 2 to 8 parts by weight, based on 100 parts by weight of the total of the components (a), (b) and (c). .
If it is less than 0.5 parts by weight, the effect of addition is small, and if it exceeds 20 parts by weight, mechanical strength such as impact strength is lowered. The flame-retardant resin composition of the present invention, other components as long as it does not impair the moldability and physical properties, such as pigments, dyes, colorants,
Organic reinforcing materials, heat-resistant agents, stabilizers typified by copper compounds and hindered phenol compounds, antioxidants, photoprotective agents, weathering agents, light stabilizers, crystal nucleating agents, lubricants, release agents. It is free to add and introduce a plasticizer, an antistatic agent, or the like.

Furthermore, the flame-retardant resin composition of the present invention comprises
Depending on the performance required from the application, other polymers such as polyptadiene (PB), polyethylene (PB)
E), ethylene-propylene copolymer (EP and EP
DM), butadiene-styrene copolymer, styrene-ethylene-butene-styrene copolymer (SEBS), acrylic rubber (AR), fluororubber (FR), acrylonitrile
-Butadiene-styrene copolymer (ABS), acrylonitrile-ethylene propylene-styrene copolymer (AE
S), acrylonitrile-styrene copolymer (AS),
Polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Polyester mixture, Polycarbonate (PC), Polysulfone, Polyether sulfone (PES), Polyimide (PI), Polyphenylene sulfide (PPS), Polyether ether ketone (PEEK), Vinylidene fluoride polymer (PVDF, etc.) , Polyoxymethylene (P
OM), polytetrafluoroethylene (PTFE), polyphenylene ether (PPE), polyamides other than nylon 4,6, crosslinked particles, and modified products thereof, 100 parts by weight of the flame-retardant resin composition of the present invention. Against 50
The amount can be appropriately mixed in an amount not more than 30 parts by weight, more preferably less than 30 parts by weight. The flame-retardant resin composition of the present invention is used for conventional thermoplastic resins such as known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding and compression molding of the above resin composition. By subjecting to molding, various molded products can be molded.

The flame-retardant resin composition of the present invention can be particularly preferably used as, for example, electronic parts, heat-resistant containers, filters and the like. Here, what is referred to as an electronic component is a main body of various connectors, switches, relays, coil bobbins, volumes, sockets, plug boards, terminal blocks, sensors, resistors, transformers, ICs (integrated circuits), etc. Or, mainly, housing (case, body, cover), frame, electric insulator, slide (slider), base, wafer, lens cam, spool, cover.
Typical examples are do and yoke. Among them, what is referred to as a connector may be any of a wire-to-wire (relay) connector-, a wire-to-board connector-, a board-to-board connector, etc., and an FFC / FPC connector-, a SIMM socket, a ROM. Connector, interface connector, card edge connector, disk drive power connector, board-in connector, jumper-wire connector, etc. , Straight type, right angle type, multi-hears type, eject lever type, clip mounting type, bottom entry type, strain relief, etc., the connection form is stack connection, horizontal connection, vertical connection. Any of The connector of the present invention is a main body of the above-mentioned various connectors, or mainly a housing (case, body, cover), frame, electrical insulator, slide (slider), base, wafer, Representative examples include materials used as Rencam, spool, card, yoke, eject pin, eject lever and the like. Here, what is referred to as a heat-resistant container is used in homes, various dining rooms, coffee shops, automobiles, shared vehicles (buses, taxis, etc.), trains, aircraft, ships (passenger ships including small ships, etc.), etc. Examples include trays, trays for heating food, containers for heating and transporting towels, towels, sheets, clothes, baskets, tableware such as cups, cups, and bowls, and heat-resistant containers such as ashtrays. . Here, as what is called a filter,
In addition to an oil filter and a strainer provided in a vehicle engine oil lubrication system, and in addition to an engine oil lubrication system, for example, in the middle of a brake oil circulation pipe,
It can also be used in a transmission, a fuel tank inlet / outlet, a clutch master-cylinder, and the like. Also,
It is not limited to a filter for oil, but can be suitably used as a filter for air or the like. Further, it can be suitably used as various filters for household appliances, various filters for industrial electric appliances, and various filters for industrial members (for example, hydraulic control system of construction machinery, lubrication system, etc.).

[0010]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The following materials were used in the examples and comparative examples. Component (a): Nylon 4,6 "Stanyil" manufactured by DSM Co., Netherlands, relative viscosity 3.0 at 96% sulfuric acid 1 g / dl was used. Component (b): b-1: polybrominated styrene, bromine content 59% by weight,
Number average molecular weight Mn = 21,000, Mw / Mn = 1.86 b-2: Post-brominated polystyrene, bromine content 67% by weight, number average molecular weight Mn = 84,000, Mw / Mn = 2.
39 b-3: Post-brominated polystyrene, bromine content 58% by weight, number average molecular weight Mn = 32,000, Mw / Mn = 6.
12 b-4: Post-brominated polystyrene, bromine content 59% by weight, number average molecular weight Mn = 120,000, Mw / Mn =
3.3 Component (c): Anti-dripping agent: c-1: Ethylene / glycidyl methacrylate copolymer: Ethylene / glycidyl methacrylate (epoxy group-containing) = 85/15 (weight ratio) Polymer. c-2: Butadiene / styrene copolymer hydrogenated maleic anhydride adduct (maleic anhydride modified styrene / ethylene / butene copolymer): styrene / ethylene / butene = 20/80 (weight ratio) Coalescence, acid value 10mgC
H ₃ ONa / g. c-3: Maleic anhydride-modified ethylene / propylene copolymer: maleic anhydride / ethylene / propylene = 1/9
9 (weight ratio) copolymer. c-4: Styrene / maleic anhydride copolymer: a copolymer of styrene / maleic anhydride = 70/30. c-5: Epoxy resin: number average molecular weight of about 1500 (10
00-2000), epoxide amount 500-2000mm
ol / kg. Component (d): Inorganic filler: Glass fiber, diameter about 10 μm
3 m average length made from strands of continuous filaments
m chopped strands.

The performance of the samples described in Examples and Comparative Examples was measured by the following method. Deflection temperature under load: According to ASTM D648. (Load 18.6 kg / cm ²⁾ Evaluation item regarding heat resistance. Izod impact strength: According to ASTM D256. Thermobalance analysis (Thermogravimetric
(Analysis; TGA): Weight loss rate after 30 minutes when the temperature was kept at 315 ° C in nitrogen. Evaluation items regarding thermal stability. Flexural modulus: According to ASTM D790. Bending speed 15 mm / min. Evaluation item for rigidity. Flame retardance: According to UL-94 test method, using a test piece of 1/32 inch thickness, a combustion test (Vertical T
est) was performed to determine V-0 or V-2. However, in the combustion test, V-0 means that there is no melt dripping of the resin, or that there is melt dripping of the resin but does not ignite the cotton placed below, V-2
Is the case where there is molten dripping of resin and the cotton placed below is ignited. Dripping: In the above combustion test, the presence or absence of molten dripping of the resin was visually determined. (With melt dripping is represented by x, without melt dripping.) As examples and comparative examples, the compositions and evaluation results of the above items are shown in Tables 1 to 3 below.

Examples 1 to 7 Evaluations were made by the above-mentioned methods, and the results shown in Table 1 were obtained. Table 1
From the results shown in, the flame-retardant resin composition of the present invention is excellent in heat resistance, impact resistance, thermal stability at the time of molding, and has a large dripping phenomenon (flame drop dropping phenomenon) at the time of combustion. You can see that it has been improved to.

[0013]

[Table 1]

Comparative Examples 1 to 11 Evaluations similar to those in Examples were carried out, and the results shown in Table 2 were obtained.

[0015]

[Table 2]

Comparative Example 1 is a case where the amount of the component (b) used in the present invention exceeds the claimed range, and the excellent performance of nylons 4 and 6 is impaired, and the deflection temperature under load, impact strength, and flexural modulus are reduced. , Was inferior, and a dripping phenomenon was observed. In Comparative Example 2, the amount of the component (b) of the present invention used was less than the claimed range, and the flame retardancy was lowered. Comparative Examples 3 to 5 are cases in which post-brominated polystyrenes having different molecular weights and molecular weight distributions were used as the component (b) of the present invention, and Example 2 was used.
The impact strength and thermal stability are inferior compared to. Comparative Example 6
And 7 have the same composition as in Example 2 and Comparative Example 3 and use nylon 6,6 instead of nylon 4,6 (however, the melting points of nylon 4,6 and nylon 6,6 are 295 ° C. respectively). , 262 ° C. and about 30 ° C., the temperature during extrusion and injection molding was lower than that of nylon 4,6 by about 30 ° C. In the thermobalance analysis, the same analysis was performed by setting the temperature to 285 ° C.) Nylon 4, Unlike the case of 6, the processing temperature was lower than 300 ° C., and therefore no difference was found depending on the type of flame retardant. Comparative Example 8 is the case where the amount of the component (c) of the present invention used is less than the claimed range, the flame retardance is poor, and the dripping phenomenon is also observed. In Comparative Example 9, the amount of the component (c) used in the present invention exceeded the claimed amount, and the deflection temperature under load, impact strength, and flexural modulus were poor.
Comparative Example 10 is a case where the amount of the component (d) used in claim (2) of the present invention exceeds the claimed amount, and extrusion processing (pelletization) could not be performed.

[0017]

EFFECTS OF THE INVENTION Nylon 4 and 6 have a higher melting point than other nylons and a high molding temperature. Therefore, in the flame retardant method using the flame retardant used for conventional nylon 6, nylon 6,6 and the like, problems such as deterioration of heat resistance, impact strength and thermal stability have been observed. In the present invention,
As a flame retardant, polybrominated styrene obtained by polymerizing a brominated monomer and having a number average molecular weight and a molecular weight distribution (Mw / Mn) within a specific range is used, whereby the above-mentioned problems are significantly reduced. I was able to improve. Furthermore, by adding an anti-dripping agent, the dripping in the combustion test could be significantly improved. Therefore,
The flame-retardant resin composition of the present invention has greatly improved the above-mentioned problems and is excellent in heat resistance, impact resistance, and thermal stability at the time of molding, and further, dripping phenomenon at combustion (dripping phenomenon of flame particles). ) Is greatly improved and the flame retardancy is also excellent, so that it can be applied to applications in which the excellent performance of nylon 4 and 6 can be fully exhibited, and the industrial value is extremely high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Nihon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] 1. (a) 50 to 96.9 of nylon 4,6
%, Obtained by polymerizing (b) brominated styrene monomer and having a number average molecular weight (Mn) of 1 × 10 ^{4 to} 9 × 10 ^4.
3 to 45% by weight of polybrominated styrene having a weight average molecular weight (Mw) / number average molecular weight Mn ratio of 5 or less, and (c) 0.1 to 5% by weight of a dripping inhibitor. A flame-retardant resin composition comprising: 2. (a) 50 to 9 of nylon 4,6
6.9% by weight, (b) obtained by polymerizing brominated styrene monomer, and having a number average molecular weight (Mn) of 1 × 10 ^{4 to} 9
× a 10 ^4, weight average molecular weight (Mw) / number ratio of the average molecular weight Mn is 5 or less polybrominated styrene 3-4
5 wt%, (c) 0.1-5 wt% anti-dripping agent, and (d) inorganic fillers (a), (b), (c).
The flame-retardant resin composition is contained in an amount of 1 to 200 parts by weight with respect to 100 parts by weight as a total amount.