JPH034584B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic resin composition containing a halogenated flame retardant that is stabilized. Thermoplastic resins such as polyolefin resins, styrene resins, polyester resins, nylon resins, polyacetal resins, and polycarbonate resins have excellent physical properties and are therefore used in a variety of applications, such as electrical appliances, interior decoration products, and building materials. ing. However, since thermoplastic resins are flammable, flame retardant regulations are imposed depending on their use. To make the thermoplastic resin flame retardant, a flame retardant such as a polychlorinated organic compound, a polybrominated organic compound, antimony trioxide, or a phosphorus compound is added. Among them, halogen flame retardants such as polychlorinated organic compounds and polybrominated organic compounds are effective and often used. However, halogen flame retardants are unstable at high temperatures and easily decompose, so thermoplastic resins containing them become colored during processing. In particular, since the above-mentioned thermoplastic resin has a high processing temperature (200°C or higher), this phenomenon is remarkable. Therefore, in order to prevent coloration caused by these flame retardants, methods of adding metal salts of dehydroacetic acid (Japanese Patent Application Laid-Open No. 79046/1982) and methods of adding dialkyltin malate polymers (Japanese Patent Publication No. 47-2209) have been proposed. However, none of them have sufficient thermal stability at high temperatures, and there is a need for the development of an excellent stabilizer that can prevent this thermal deterioration. As a result of various studies, the present inventors have discovered that adding aluminum acrylate or methacrylate can thermally stabilize thermoplastic resins containing halogenated flame retardants even during high-temperature processing. It has arrived. That is, the present invention provides a resin composition comprising 100 parts by weight of a resin selected from polyolefin resin, styrene resin, polyester resin, nylon resin, polyacetal resin, and polycarbonate resin and 1 to 50 parts by weight of a halogen flame retardant. This is a stabilized flame-retardant thermoplastic resin composition characterized in that 0.01 to 5 parts by weight of aluminum acrylate and/or aluminum methacrylate are added when thermally stabilizing the combustible resin. Further, the present invention provides a method for thermally stabilizing the flame retardant resin by combining (a) 0.01 to 5 parts by weight of aluminum acrylate or/and aluminum methacrylate and (b) dialkyltin malate polymer or/and dialkyltin malate polymer. This is a stabilized flame-retardant thermoplastic resin composition characterized by adding 0.01 to 5 parts by weight of a rate ester salt. Examples of thermoplastic resins to be made flame retardant in the present invention include polyolefin resins such as polyethylene and polypropylene, polystyrene, methylstyrene mainly composed of styrene, divinylbenzene, butazinine, copolymers with acrylonitrile, and acrylonitrile-butadiene-styrene. Ternary copolymer, acrylonitrile/butadiene/
Styrenic resins such as methylstyrene terpolymers, mixtures of copolymers of butadiene and styrene or acrylonitrile, and copolymers of styrene and acrylonitrile; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, e.g. nylon 6; ,Nylon
Mention may be made of nylon resins such as 66, nylon 11, nylon 12, polyacetal resins such as acetal homopolymers, acetal copolymers, and polycarbonate resins. In the present invention, halogen-based flame retardants such as polychlorinated organic compounds and polybrominated organic compounds are used to make the thermoplastic resin flame retardant. Examples of polychlorinated organic compounds include polychloroparaffin, chlorinated polyethylene, perchloropentacyclodecane, tetrachlorophthalic anhydride, chlorendoic acid, hexachloroethane, hexachlorocyclohexane, pentachlorobenzene, etc. Examples of compounds include bromides of aliphatic hydrocarbons such as tetrabromoethane, tetrabromobutane, and tribromopropane, tribromotrichlorocyclohexane, tetrabromodichlorocyclohexane, pentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, and bis. Bromides of alicyclic hydrocarbons such as (dibromocyclohexyl)-1,2-dibromoethane, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether,
Hexabromodiphenyl ether, pentabromodiphenyl ether, pentabromotoluene, pentabromoethylbenzene, pentabromophenol, tribromophenol, 1,2-dibromopropyl tribromophenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, tetrabromophthalic anhydride, 1,2-
Examples include aromatic bromides such as bis(pentabromophenoxy)ethane, bis(tribromophenoxy)ethane, and polydibromophenylene oxide, and carbonate oligomers of tetrabromobisphenol A. The amount of the halogen flame retardant added is 1 to 50 parts by weight, and the amount of aluminum acrylate and/or aluminum methacrylate added is 0.01 to 5 parts by weight relative to 100 parts by weight of the thermoplastic resin. (meta)
If the amount of aluminum acrylate added is less than the lower limit, thermal stabilization will be insufficient, and if the amount is more than the upper limit, it will be uneconomical. Although the flame-retardant thermoplastic resin of the present invention can be sufficiently thermally stabilized with aluminum acrylate or aluminum methacrylate, if a higher degree of thermal stability is required, dialkyltin malate polymer or dialkyltin malate may be used. Addition of ester salts achieves this purpose. Dialkyltin malate polymers have the general formula (In the formula, R represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 2 to 10.) In addition, dialkyltin malate ester salt has the general formula

[Formula] R ₂ Sn (OOCCH=CHCOOR') ₂ (In the formula, R is an alkyl group or alkoxycarbonylethyl group having 1 to 12 carbon atoms, and R' is an alkyl group, alkenyl group, aralkyl group, or cycloalkyl group. or a methoxybutyl group). In the above formula, the R group includes, for example, a methyl group, a butyl group, an octyl group, a dodecyl group, a methoxycarbonylethyl group, an ethoxycarbonylethyl group, a butoxycarbonylethyl group, and the R' group includes, for example, a butyl group and an octyl group. , isooctyl group, 2-ethylhexyl group, lauryl group, stearyl group, myristyl group, cetyl group, behenyl group,
Examples include oleyl group, benzyl group, cyclohexyl group, and methoxybutyl group. In the present invention, the amount of the dialkyltin malate polymer or dialkyltin malate ester salt added is 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic resin. If the amount added is less than the lower limit, the thermal stability will not be improved, and if the amount is more than the upper limit, it is uneconomical. The composition of the present invention may optionally contain an antioxidant,
UV absorbers, boric acid, boric acid esters, epoxy compounds, metal soaps, diketone compounds, non-halogen flame retardants (e.g. phosphorus compounds, antimony trioxide, borates, aluminum hydroxide, etc.),
Smoke removers (smokeless agents), pigments, fillers, lubricants, etc. can be added. According to the present invention, a thermoplastic resin containing a halogen flame retardant can be highly thermally stabilized, and the core resin can be easily processed at high temperatures. Addition of dialkyltin malate polymer or dialkyltin maleate ester salt further improved thermal stability. Such an effect cannot be achieved with other metal salts of carboxylic acids. Next, the present invention will be explained with reference to Examples, in which parts by weight are indicated. Example 1 100 parts of acrylonitrile-butadiene-styrene resin (Toughflex 450, manufactured by Mitsubishi Monsanto),
Add 25 parts of tetrabromobisphenol A, 5 parts of antimony trioxide, and 0.3 parts of the stabilizer shown in Table 1 below, and mix with a kneading roll for 4 minutes at 150°C to form a mixture with a thickness of 0.5
A sheet of mm was created. About this sheet
Thermal stability tests were conducted in a gear oven held at 220°C. The numbers in the table represent the following evaluations. 1: White Color 2: Light yellow 3: Yellow 4: Light brown 5: Brown 6: Dark brown The results are shown in Table 1.

【table】

[Table] Example 2 Styrene resin (Styron 666, manufactured by Asahi Kasei Corporation)
100 parts, 15 parts of hexabromocyclododecane, 1 part of titanium oxide, and 0.5 parts of the stabilizer shown in Table 2 below.
% and mixed with a kneading roll for 3 minutes at 135℃,
A sheet with a thickness of 0.5 mm was created. This sheet was subjected to a thermal stability test in a gear oven maintained at 220°C. The numbers in the table represent the following evaluations. 1: White 2: Light yellow 3: Yellow 4: Light brown 5: Light blackish brown 6: Blackish brown The results are shown in Table 2.

[Table] Example 3 100 parts of polypropylene resin (E-100G, manufactured by Idemitsu Petrochemical Co., Ltd.), perchloropentacyclodecane
20 parts of antimony trioxide, 10 parts of antimony trioxide, and 0.2 parts of the stabilizer shown in Table 3 below were added and mixed at 180°C for 3 minutes using a kneading roll to form a sheet with a thickness of 0.5 mm.
This sheet was subjected to a thermal stability test in a gear oven maintained at 220°C. The numbers in the table represent the following evaluations. 1: White 2: Light yellow 3: Yellow 4: Light brown 5: Brown 6: Dark brown The results are shown in Table 3.

[Table] Example 4 100 parts of polyester resin (Tuffpet N1000, manufactured by Mitsubishi Rayon Co., Ltd.), carbonate oligomer of tetrabromobisphenol A (Fireguard)
7000, manufactured by Teijin Chemicals) 10 parts, antimony trioxide 3
1 part and 1.0 part of the stabilizer shown in Table 4 below, mixed with a Henschel mixer, and extruded using a 20 mm extruder (extrusion conditions: cylinder temperature, C ₁ 210℃, C ₂ 230
A sheet with a thickness of 1 mm was produced by extrusion at a die temperature of 240°C. This sheet was subjected to a thermal stability test in a gear oven maintained at 240°C. Note that the numbers in the table represent the same evaluation as in Example 1. The results are shown in Table 4.

[Table] Example 5 100 parts of nylon resin (S1040, manufactured by Unitika), polyacetal resin (Dyuracon M90, manufactured by Polyplastics) or polycarbonate resin (Panlite L1250, manufactured by Teijin Chemicals), 15 parts of octabromobiphenyl ether part, titanium oxide 0.5 part,
0.3 part or 0.5 part of the stabilizer shown in Table 5 below was added, mixed with a Henschel mixer, and extruded with a 20 mm extruder (extrusion conditions are shown below) to produce a sheet with a thickness of 1 mm. This sheet was subjected to a thermal stability test in a gear oven maintained at 240°C. Note that the numbers in the table represent the same evaluation as in Example 1. The results are shown in Table 5.

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【table】

【table】

Claims (1)

[Claims] 1. A resin selected from polyolefin resins, styrene resins, polyester resins, nylon resins, polyacetal resins, and polycarbonate resins.
When thermally stabilizing a flame retardant resin consisting of 100 parts by weight and 1 to 50 parts by weight of a halogen flame retardant, 0.01 to 5 parts by weight of aluminum acrylate or/and aluminum methacrylate is added. stabilized flame-retardant thermoplastic resin composition. 2 Resin selected from polyolefin resin, styrene resin, polyester resin, nylon resin, polyacetal resin, and polycarbonate resin
When flame-stabilizing a flame retardant resin consisting of 100 parts by weight and 1 to 50 parts by weight of a halogen flame retardant, (a) 0.01 to 5 parts by weight of aluminum acrylate or/and aluminum methacrylate and (b) A stabilized flame-retardant thermoplastic resin composition, characterized in that 0.01 to 5 parts by weight of a dialkyltin malate polymer or/and a dialkyltin malate ester salt is added.