JPH09227776A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin composition, having extremely improved thermal stability as compared with that of a conventional one by blending a specific flame retardant therein and remarkably improved in dripping phenomena at the time of burning by addition of a specified fluorine-based polymer thereto. SOLUTION: This flame retardant resin composition comprises the following components (a), (b) and (c): (a) nylon 4, 6, (b) a polybrominated polystyrene, prepared by polymerizing a brominated styrene monomer and having 1×10<4> to 9×10<4> number-average molecular weight (Mn ) and <=5 ratio of the weight- average molecular weight (Mw )/Mn and (c) a fluorine-based polymer. The average particle diameter of the component (c) present in a molding product when formed into the molding product is regulated so as to provide <25μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which is excellent in thermal stability during molding and has a greatly improved dripping phenomenon (flame drop dropping phenomenon) during combustion.

[0002]

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 category of self-extinguishing when tested according to ASTM D635. However, recently, for the purpose of improving the safety of products used in general households such as household products, electric devices, building materials, automobile parts, etc., the demand for flame retardancy has become stronger,
Regulations on flame retardancy are becoming stricter. For this reason, in each country, regulatory measures are taken according to national circumstances, and test methods are being established. Underwriters Laboratories (Underwriters Laborat)
The ory (hereinafter abbreviated as UL) standard stipulates a detailed test method as well as 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 electrical equipment and the like, it is often required that the resin composition pass the V-0 standard in a combustion test according to the UL-94 test method. The UL-94 test method stipulates the burning time after flame contact, etc., but at the same time, it is also stipulated that flame particles that ignite cotton under 12 inches (305 mm) should not be dropped. Clarification of ripping phenomenon and prevention measures are strongly desired.

Examples of the method for 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, and the like. As a method of making nylon 4 and 6 flame-retardant, a method of adding a flame-retardant agent, specifically, a method of blending an organic halogen compound, is known as in many other synthetic resins. Generally, the combustion process of resin is performed by heating, melting,
Degradation / decomposition, vaporization / diffusion, ignition, and continuous combustion,
Elucidation of combustion phenomena and elucidation of flame retarding mechanism are not always sufficient because the way of manifestation differs depending on each polymer material, and especially measures to prevent dripping phenomenon (flame drop dropping phenomenon) during combustion are strong. It is desired, and in particular, in the case of nylon 4 and 6, it was a big problem because its melt viscosity was particularly low. Further, 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 by the conventional organic halogen compound, and improvement in thermal stability has been demanded. . That is, the conventional organic halogen compound is insufficient as a flame retardant for nylon 4 and 6 in terms of thermal stability, and at the same time,
As a nylon 4,6 resin composition, it was necessary to improve the dripping phenomenon during combustion.

[0004]

SUMMARY OF THE INVENTION The present invention has been made against the background of the above-mentioned problems of the prior art. By incorporating a specific flame retardant, the performance of nylon 4,6 resin is not impaired and it is extremely superior to conventional ones. With the aim of providing a flame-retardant resin composition that achieves excellent thermal stability and that the dripping phenomenon during combustion is significantly improved by the addition of a fluoropolymer having a specific particle size in the molded body. To do.

[0005]

The present invention provides (claim 1)
Consists of the following (a), (b), and (c) components,
A flame-retardant resin composition, characterized in that the component (c) present in the molded body has an average particle size of less than 25 microns. (A) Nylon 4,6, (b) Brominated styrene monomer
Obtained by polymerizing and having a number average molecular weight (Mn) of 1 × 1.
Polybrominated styrene having a weight average molecular weight (Mw) / Mn of 0 ^{4 to} 9 × 10 ⁴ and 5 or less, (c) a fluoropolymer.
And (claim 2) the following (a), (b),
The average particle size of the component (c), which is composed of the components (c) and (d) and is present in the molded product when the molded product is 25,
A flame-retardant resin composition characterized by having a size of less than micron. (A) Nylon 4,6, (b) Obtained by polymerizing brominated styrene monomer, and having a number average molecular weight (Mn) of 1 × 10 ^{4 to} 9 × 10 ⁴ and a weight average molecular weight (Mw) / Mn of Polybrominated styrene having a ratio of 5 or less, (c) a fluoropolymer. (D) 1 to 100 parts by weight of the total amount of (a) to (c)
To 200 parts by weight of inorganic filler.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Nylon 4,6 as the component (a) used in the present invention is polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid, and mainly contains polytetramethylene adipamide units. It contains a copolyamide as a 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, ε-caprolactam,
Lactams such as ω-lauryllactam, hexamethylenediamine, 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 , Dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 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
-83029 and Japanese Patent Application Laid-Open No. 61-43631, that is, first, a prepolymer having a small number of cyclic end groups is produced under specific conditions, and then this is subjected to solid phase polymerization in a steam atmosphere. There is a method of preparing high-viscosity nylon 4,6 or a method of obtaining it by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone. Although the degree of polymerization of nylon 4,6 is not particularly limited, nylon 4,6 having a relative viscosity in the range of 2.0 to 6.0 at 1 g / dl in 96% sulfuric acid at 25 ° C. is preferably used. . The blending amount of the component (a) nylon 4,6 resin in the present invention is preferably 50 to 97% by weight, more preferably 55 to 96% by weight, and further preferably, based on the total amount of (a) and (b). 60 to 95% by weight, particularly preferably 65 to 94% by weight. If the blending amount of the component (a) is too small, the excellent performance (deflection temperature under load, etc.) of the component (a) is impaired, and if the blending amount of the component (a) is too large, the blending amount of the component (b) results. The flame retardancy is poor because it is too small.

The polybrominated styrene of the component (b) of the present invention is one type of brominated styrene monomer such as monobrominated styrene, dibrominated styrene and tribrominated styrene, or
Obtained by polymerizing two or more kinds, preferably 50% by weight or more, more preferably 55% by weight of dibrominated styrene unit.
The above is polybrominated styrene. The polybrominated styrene of the present invention may, of course, be a polymer mainly of dibrominated styrene monomer, but a copolymer of dibrominated styrene monomer and tribrominated styrene monomer also has a bromine content. It is preferable in that it goes up. The bromine content in the polybrominated styrene is preferably 40 to 75% by weight, more preferably 50 to 75% by weight. Also,
At the time of polymerization of the brominated styrene monomer, another copolymerizable monomer may be used if necessary. Examples of the copolymerizable monomer include olefin and vinyl,
It may contain a functional group. As olefin and vinyl, ethylene, propylene, butadiene, butene,
Hexene, pentene, methylebutene, methylpentene, styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like, ethylene, propylene, butadiene, styrene,
Acrylonitrile is preferred. The functional group that the copolymerizable monomer may contain, for example, a carboxyl group,
1 selected from acid anhydride group, oxazoline group and epoxy group
Examples of the functional group include two or more functional groups, and specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic anhydride, vinyl oxazoline, glycidyl methacrylate, allyl glycidyl ether and the like. Can be mentioned. Alternatively, the above-mentioned functional group may be copolymerized with brominated styrene, or the terminal of polybrominated styrene may be modified. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and the flame retardant was 1 mg / ml.
Dissolved at a concentration of 1.0 ml / min, temperature 36-4
By measuring at 0 ° C., the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) can be obtained. The number average molecular weight (Mn) of the polybrominated styrene of the present invention is 1 × 10 ^{4 to} 9 × 10 ⁴ , preferably 1
× 10 ^{4 to} 7 × 10 ⁴ , more preferably 1 × 10 ^{4 to} 5
× 10 ⁴ , and particularly preferably 1.2 × 10 ⁴ to 4 × 10 ⁴ . On the other hand, the weight average molecular weight (Mw) / Mn is 5 or less,
It is preferably 1 to 4, more preferably 1.1 to 3.5, and particularly preferably 1.2 to 3. The present invention is a polybrominated styrene obtained by polymerizing brominated styrene monomer as a flame retardant, using nylon 4,6 as a polyamide resin, and having a number average molecular weight and Mw / Mn within the above-mentioned ranges. Is achieved by using When a polybrominated styrene having a number average molecular weight (Mn) and Mw / Mn outside the range of the present invention is used, thermal stability, dripping property, performance of nylon 4,6 resin composition (impact strength, The performance of at least one of the deflection temperatures under load, etc.) cannot reach the object of the present invention. Further, when brominated polystyrene obtained by brominating polystyrene later is used as the flame retardant, the thermal stability is poor even when the number average molecular weight or Mw / Mn is in the above range, and the object of the present invention is Can not be achieved. The blending amount of the component (b) polybrominated styrene of the present invention is preferably 3 to 50% by weight, more preferably 4 to 45% by weight, and further preferably, based on the total amount of the components (a) and (b). 5 to 40% by weight, particularly preferably 6 to 35% by weight. If the blending amount of the component (b) is too small, the flame retardancy is poor, and if the blending amount of the component (b) is too large, the excellent performance of the component (a) (deflection temperature under load, etc.).
Is damaged.

The fluoropolymer of the component (c) of the present invention serves as an anti-dripping agent. The fluorinated polymer is a polymer having a carbon-fluorine bond in the molecule, and as a representative example, a vinylidene fluoride polymer (polyvinylidene fluoride; PVDF, etc.), polyvinyl fluoride (PV
F), ethylene / chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (P
CTFE), ethylene / tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), perfluoromethyl vinyl ether (PFMV), tetrafluoroethylene / fluoroalkyl vinyl ether Tercopolymer (PF
A), tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer,
Examples thereof include polytetrafluoroethylene (PTFE) and fluororubber. The manufacturing method is not particularly limited,
Bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method, a method of pressing a monomer into water containing a polymerization initiator, a method of polymerizing by ionizing radiation irradiation, and the like, a suspension polymerization method, or The emulsion polymerization method is preferred. In addition, the average particle size of the fluoropolymer component in the molded product by microscopy is 2
It is less than 5 μm, preferably 23 μm or less, and more preferably 0.5 to 20 μm. The average particle size in the compact is 25μ
If it is more than m, the effect as an anti-dripping agent is hardly recognized. When using the component (c), it is necessary to appropriately select the particle size of the fluoropolymer used so that the average particle size in the molded product falls within the above range. However, when used with nylon 4,6 resin In addition, mixing conditions (processing conditions) are also important. That is, it is preferable to uniformly and finely mix the nylon 4,6 resin having a melting point of 295 ° C in a molten state in consideration of the melting point of the fluoropolymer (for example, about 330 ° C for PTFE). Nylon 4,
Unlike many other resins, the 6-resin has a processing temperature and a melting point of the fluoropolymer which are relatively close to each other throughout the processing such as extrusion processing and injection processing, and the fluoropolymer after processing depends on the mixing conditions. This is because the particle size of the may change greatly. The blending amount of the fluoropolymer of the component (c) of the present invention is preferably 0.01 to 4 parts by weight, more preferably 0.04 parts by weight, based on 100 parts by weight of the total amount of (a) and (b). 02 to 3 parts by weight, more preferably 0.
03 to 2.5 parts by weight, particularly preferably 0.05 to 2 parts by weight. If the blending amount of the component (c) is too small, the effect as a dripping inhibitor is not recognized, and if the blending amount of the component (c) is too large, the excellent performance (impact strength etc.) of the component (a) is deteriorated. Resulting in.

In the flame-retardant resin composition according to the second aspect, the inorganic filler is an essential component as the component (d) in addition to the components (a), (b) and (c). By using the component (d), 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, and typical examples are 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 balun (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,
Examples thereof include metal whiskers. For the purpose of the present invention, glass fiber, carbon fiber, kaolin, mica, talc are preferred, and especially glass fiber from its economical efficiency,
Kaolin, mica and talc are preferred. 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 1 to 200 parts by weight, preferably 2 to 180 parts by weight, based on 100 parts by weight of the total amount of the constituent components (a) and (b) of the present invention, More preferably 3 to 15
0 parts by weight, particularly preferably 5 to 120 parts by weight. If the amount of the inorganic filler added is less than 1 part by weight, the purpose of adding the component (d) will not be achieved, while if it exceeds 200 parts by weight, processability, particularly extrusion moldability and injection moldability will deteriorate, which is not preferable.

If necessary, a flame retardant aid may be added to the flame retardant resin composition according to the first and second aspects 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 addition amount of the flame retardant aid is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and particularly preferably 100 parts by weight of the components (a) and (b). It is 1 to 10 parts by weight. If it is less than 0.1 parts by weight, the purpose of addition is not achieved, and if it exceeds 20 parts by weight, mechanical strength such as impact strength is lowered, which is not preferable.

The flame-retardant resin composition of the present invention contains other components such as pigments, dyes, colorants, organic reinforcing materials, heat-resistant agents, copper compounds and hindered phenol as long as the moldability and physical properties are not impaired. -Introduce a stabilizer represented by a compound, an antioxidant, a photoprotective agent, a weathering agent, a light stabilizer, a crystal nucleating agent, a lubricant, a release agent, a plasticizer, an antistatic agent, etc. Is free.

Further, 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), allyl rubber (AR), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene propylene-styrene copolymer (AES), acrylonitrile-styrene copolymer (AS), polystyrene (P
S), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester mixture, liquid crystal resin (LCP), polycarbonate (PC),
Polysulfone, polyethersulfone (PES), polyimide (PI), polyphenylene sulfide (PP)
S), polyether ether ketone (PEEK), polyoxymethylene (POM), polyphenylene ether (PPE), polyamides other than nylon 4,6, crosslinked particles and the like, and modified products thereof. 100 parts by weight or less, preferably 50 parts by weight or less, and more preferably 1 to 30 parts by weight can be mixed with 100 parts by weight of the flame-retardant resin composition.

The flame-retardant resin composition of the present invention is prepared by subjecting the above resin composition to conventional thermoplastic resins such as known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding and compression molding. Various molded products can be obtained by subjecting the molded product to the molding process. INDUSTRIAL APPLICABILITY The flame-retardant resin composition of the present invention is used in various fields requiring flame retardancy in the fields of electric and electronic, vehicle, machine, OA equipment, sundries (for example, electronic parts, vehicle parts, machine parts, OA). It can be preferably used for equipment parts, heat resistant containers, filters, etc.).

[0014]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The following materials were used in the examples and comparative examples. Component (a): a-1: As nylon 4,6, "Stanyl" manufactured by DSM, Netherlands, and relative viscosity 3.0 at 96% sulfuric acid 1 g / dl were used. a-2: Amylan CM30 manufactured by Toray as nylon 6,6
01 was used in the comparative example.

Component (b): b-1: polybrominated styrene, bromine content 61% by weight, number average molecular weight Mn = 21,000, Mw / Mn = 1.8
6, a polymer of dibromostyrene. b-2: Polybrominated styrene, bromine content 68% by weight, number average molecular weight Mn = 30,000, Mw / Mn = 2.1
3, a copolymer of dibromostyrene: tribromostyrene = 2: 8. b-3: Modified polybrominated styrene, bromine content 60% by weight, number average molecular weight Mn = 52,000, Mw / Mn = 1.9
2. Copolymer of maleic anhydride (2wt%) and dibromostyrene. b-4: Post-brominated polystyrene, bromine content 67% by weight, number average molecular weight Mn = 84,000, Mw / Mn = 2.3
9. b-5: Post-brominated polystyrene, bromine content 58% by weight, number average molecular weight Mn = 32,000, Mw / Mn = 6.1
2. b-6: Post-brominated polystyrene, bromine content 59% by weight, number average molecular weight Mn = 120,000, Mw / Mn = 3.3
0.

Component (c): c-1: PTFE, "Hostaflon TF20, Hoechst"
25 "c-2: PTFE, Asahi Glass" Fluon L169J "c-3: PTFE, Mitsui DuPont Fluorochemical" Teflon 6J "c-4: PTFE, Asahi Glass" Fluon XL169JA "c-5: Ethylene / glycidyl methacrylate Polymer: Copolymer of ethylene / glycidyl methacrylate (containing epoxy group) = 85/15 (weight ratio). c-6: Epoxy resin: number average molecular weight of about 1500 (10
00-2000), epoxide amount 500-2000mm
ol / kg.

Component (d): Inorganic filler: glass fiber, chopped strands of average length 3 mm made from strands of continuous filaments with a diameter of about 10 μm.

The performance of the samples described in Examples and Comparative Examples was measured by the following method. Thermobalance analysis (Thermogravimetric
(Analysis; TGA): Evaluation item regarding thermal stability. The processing temperature of the resin composition of the present invention during extrusion and injection molding is usually 300 to 320 ° C., and one of the features of the present invention is that there is little oxidative deterioration or thermal decomposition at the processing temperature. The thermobalance analysis is a method that can evaluate the thermal stability. The measurement conditions of the thermobalance analysis used in the present invention are that the temperature is kept at 315 ° C. in a nitrogen atmosphere, and the weight after 30 minutes has elapsed is compared with the weight before the measurement. The preferable range of the weight reduction rate is less than 8%. 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.) Deflection temperature under load: According to ASTM D648. (Load 18.6 kg / cm ²⁾ Evaluation item regarding heat resistance. Impact strength (Izod impact strength): ASTM D2
According to 56. Average particle size: The average particle size (micron) in the molded body by microscopy.

As examples and comparative examples, the compositions and the evaluation results of the above items are shown in Tables 1 and 2 below.

[0020]

[Table 1]

[0021]

[Table 2]

Examples 1 to 6 Evaluations were made by the above-mentioned methods, and the results shown in Table 1 were obtained. From the results shown in Table 1, the flame-retardant resin composition of the present invention shows that the performance of nylon 4,6 resin (deflection temperature under load, impact strength, etc.)
It can be seen that the thermal stability is excellent, and the dripping phenomenon (flame drop dropping phenomenon) at the time of combustion is significantly improved without deteriorating the temperature. In particular, it can be seen that the fluorine-based polymer as the component (c) of the present invention is effective even if the addition is less than 1%, which is not the case with conventional anti-dripping agents.

Comparative Examples 1 to 9 Evaluations similar to those in Examples were carried out, and the results shown in Table 2 were obtained. Comparative Example 1
Nos. 3 to 3 are cases where post-brominated polystyrenes having different molecular weights and molecular weight distributions were used as the component (b) of the present invention, and the impact strength and thermal stability were inferior to those of Example 2 in all cases. Comparative Examples 4 and 5 have the same composition as that of Example 2 and Comparative Example 1, except that nylon 6,6 is used in place of nylon 4,6 (however, the melting points of nylon 4,6 and nylon 6,6 are The temperature at the time of extrusion and injection molding was about 30 ° C lower than that of nylon 4.6 because the difference was 295 ° C and 262 ° C, respectively, about 30 ° C.
The same analysis was performed as. ). Nylon 4,6
Unlike the above case, since the processing temperature was lower than 300 ° C., no difference was found depending on the type of flame retardant. Comparative Example 6 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. Comparative Examples 7 to 9 are cases in which a conventional anti-dripping agent or the like outside the claims is added as the component (c) of the present invention. In Comparative Example 7, the average particle size of the used fluoropolymer in the molded body was more than 25 microns,
In Comparative Examples 8 and 9, a non-fluorine-based polymer was added, but in any case, the effect as the anti-dripping agent was not observed.

[0024]

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, the dripping in the combustion test could be significantly improved by adding a small amount of the fluoropolymer so that the average particle size in the molded body was less than 25 microns. Therefore, the flame-retardant resin composition of the present invention has greatly improved the above-mentioned problems and is excellent in thermal stability at the time of molding, and further drastically improved the dripping phenomenon (flame drop dropping phenomenon) at the time of combustion. Since it is also excellent in flame retardancy, it can be applied to applications where the excellent performance of nylon 4 and 6 can be fully exhibited, and its industrial value is extremely high.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08L 27/12 LGE C08L 27/12 LGE

Claims (2)

[Claims] 1. An average particle size of the component (c) which is composed of the following components (a), (b) and (c) and which is present in the molded product when the molded product is less than 25 microns. A flame-retardant resin composition characterized in that (A) Nylon 4,6, (b) Brominated styrene monomer
Obtained by polymerizing and having a number average molecular weight (Mn) of 1 × 1.
Polybrominated styrene having a weight average molecular weight (Mw) / Mn of 0 ^{4 to} 9 × 10 ⁴ and 5 or less, (c) a fluoropolymer. 2. An average particle diameter of the component (c) which is composed of the following components (a), (b), (c) and (d), and which is present in the molded product when the molded product is 25: A flame-retardant resin composition characterized by having a size of less than micron. (A) Nylon 4,6, (b) Obtained by polymerizing brominated styrene monomer, and having a number average molecular weight (Mn) of 1 × 10 ^{4 to} 9 × 10 ⁴ and a weight average molecular weight (Mw) / Mn of Polybrominated styrene having a ratio of 5 or less, (c) a fluoropolymer. (D) Inorganic filler (a), (b), (c) total amount 1
1 to 200 parts by weight with respect to 00 parts by weight.