JPH0546863B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a thermoplastic resin composition containing a heat-stabilized halogen flame retardant. 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. [Prior Art] To make thermoplastic resin flame retardant, flame retardants such as polychlorinated organic compounds, polybrominated organic compounds, antimony trioxide, and phosphorus compounds are 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 processing temperature of the above-mentioned thermoplastic resin is high (200° C. or higher), this phenomenon is remarkable. Therefore, in order to prevent coloring caused by these flame retardants, there is a method of adding a metal salt of dehydroacetic acid (Japanese Patent Publication No. 79046/1982) and a method of adding a dialkyltin malate polymer (Japanese Patent Publication No. 47/22090).
It has been known. [Problems to be Solved by the Invention] However, none of the above methods provide sufficient thermal stabilization at high temperatures, and there is a need for the development of an excellent stabilizer that can prevent this thermal deterioration. [Means for solving the problem] As a result of various studies, the present inventors discovered that adding type A zeolite makes thermoplastic resins containing halogenated flame retardants thermally stable even during high-temperature processing. I came up with an invention. That is, the present invention provides a flame retardant resin 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. When thermally stabilizing, the general formula (1.0±0.2)M ₂ O・Al ₂ O ₃・(1.9±0.5)SiO ₂・(0.5~
6) H ₂ O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, including Na, K, NH ₄ , Ca, Mg, Sr,
This is a stabilized flame-retardant thermoplastic resin composition characterized by adding 0.01 to 5 parts by weight of type A zeolite (Zn). In addition, the present invention provides for thermally stabilizing the flame retardant resin by combining (a) 0.01 to 5 parts by weight of A-type zeolite and (b) 0.01 to 5 parts by weight of dialkyltin malate polymer or/and dialkyltin malate ester salt. This is a stabilized flame-retardant thermoplastic resin composition characterized by the addition of. In the present invention, thermoplastic resins to be made flame retardant include polyolefin resins such as polyethylene and polypropylene, such as polystyrene, methylstyrene mainly composed of styrene, divinylbenzene, butadiene, 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, tetrachlorometallic anhydride, chlorendoic acid, hexachloroethane, hexachlorocyclohexane, pentachlorobenzene, etc. Examples include bromides of aliphatic hydrocarbons such as tetrabromoethane, tetrabromobutane, tribromopropane, tribromotrichlorocyclohexane, tetrabromodichlorocyclohexane, pentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, 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 halogen-based flame retardant added is 1 to 50 parts by weight to 100 parts by weight of the thermoplastic resin, and the amount of the halogen flame retardant added is 1 to 50 parts by weight, and the amount of the flame retardant resin is expressed by the general formula (1.0±0.2) M ₂ O・Al ₂ O ₃・(1.9±0.5) _SiO2・(0.5～
6) H ₂ O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, including Na, K, NH ₄ , Ca, Mg, Sr,
The amount of A-type zeolite (Zn) added is 0.01 to 5.
Parts by weight. Here, when M is a monovalent cation, M ₂ O is Na ₂ O, K ₂ O, (NH ₄ ) ₂ O, respectively.
, and when M is an equivalent polyvalent cation, M ₂ O is CaO, MgO, SrO,
Let it represent ZnO. If the amount of A-type zeolite added is below the lower limit, thermal stabilization will be insufficient.
Furthermore, use of more than the upper limit is uneconomical. The flame-retardant thermoplastic resin of the present invention can be sufficiently thermally stabilized with A-type zeolite, but if a higher degree of thermal stability is required, dialkyltin maleate polymer or dialkyltin maleate ester salt may be added. That purpose will be achieved. 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.) Dialkyltin malate ester salts have the general formula R ₂ Sn (OOCCH=CHCCR′) ₂ or (In the formula, R represents an alkyl group or an alkoxycarbonylethyl group having 1 to 12 carbon atoms, and R' represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or a methoxybutyl group, respectively.)
It is expressed as 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, an ethyl group and a butyl group. , heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, lauryl group, stearyl group, myristyl group, cetyl group, behenyl group, oleyl group,
Examples include a benzyl group, a cyclohexyl group, and a methoxybutyl group. In the present invention, the amount of the dialkyltin maleate polymer or dialkyltin maleate 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,
Ultraviolet absorbers, boric acid, boric acid esters, epoxy compounds, metal soaps, diketone compounds, organic phosphorus compounds, non-halogen flame retardants (e.g. phosphorus compounds, antimony trioxide, borates, aluminum hydroxide, etc.), extinguishers. Smoke agents (smokeless agents), pigments, fillers, lubricants, etc. can be added. [Function] According to the present invention, a thermoplastic resin containing a halogen flame retardant can be highly thermally stabilized, and the resin can be easily processed at high temperatures. Addition of dialkyltin malate polymers or dialkyltin maleate ester salts further improves thermal stability. [Example] Next, the present invention will be explained with reference to Examples, where parts in the Examples indicate parts by weight. Example 1 100 parts of acrylonitrile-butadiene-styrene resin (Cycolac 211, manufactured by Ube Cycon Co., Ltd.),
Add 20 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 color 6: Dark brown The results are shown in Table 1.

[Table] Example 2 Styrene resin (Styron 666, manufactured by Asahi Kasei Corporation)
100 parts, 25 parts of hexabromocyclododecane, 1 part of titanium oxide, and 0.7 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 Color 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 1.0 part 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 color 2: Light yellow 3: Yellow color 4: Light brown color 5: Brown color 6: Dark brown color The results are shown in Table 3.

[Table] Example 4 100 parts of polyester resin (Tough Pellet N1000, manufactured by Mitsubishi Rayon Co., Ltd.), 15 parts of carbonate oligomer of tetrabromobisphenol A (Fire Guard 7000, manufactured by Teijin Kasei Co., Ltd.), 3 parts of antimony trioxide, and Table 4 below. Add 1.5 parts of the stabilizer shown in and mix in a Henschel mixer and in a 20mm 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. A thermal stability test was conducted on this sheet in a gear oven maintained at 230°C. Note that the numbers in the table represent the same evaluation as in Example 1. The results are shown in Table 4.

【table】

[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 Kasei), 10 parts of octabromobiphenyl ether 0.5 parts of titanium oxide and 0.5 parts of the stabilizer shown in Table 5 below were added, mixed in a Henschel mixer, and extruded in a 20 mm extruder (extrusion conditions are shown below) to form a sheet with a thickness of 1 mm. This sheet was subjected to a thermal stability test in a gear oven maintained at 235°C. Note that the numbers in the table represent the same evaluation as in Example 1. The results are shown in Table 5.

【table】

〔Effect of the invention〕

As is clear from the thermal stability test results of each of the above examples, in the present invention, A
Addition of type zeolite shows excellent thermal stability, and addition of dialkyltin malate polymer or/
Thermal stability was further improved by adding dialkyltin malate ester salt. These effects can only be achieved by the configuration of the present invention.

Claims (1)

[Claims] 1. Heat-stabilized flame-retardant resin consisting of 100 parts by weight of a resin selected from polyolefin resin, polyester resin, nylon resin, polyacetal resin, and polycarbonate resin and 1-50 parts by weight of a halogen flame retardant. In doing so, the general formula (1.0±0.2)M ₂ O・Al ₂ O ₃・(1.9±0.5)SiO ₂・(0.5−
6) H ₂ O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, including Na, K, NH ₄ , Ca, Mg, Sr,
1. A stabilized flame-retardant thermoplastic resin composition characterized by adding 0.01 to 4 parts by weight of type A zeolite (Zn). 2. When thermally stabilizing a flame retardant resin consisting of 100 parts by weight of a resin selected from polyolefin resin, polyester resin, nylon resin, polyacetal resin and polycarbonate resin and 1-50 parts by weight of a halogen flame retardant, (a) General formula (1.0±0.2 _{) M2O}・_Al2O3・(1.9±0.5) _SiO2・(0.5−
6) H ₂ O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, including Na, K, NH ₄ , Ca, Mg, Sr,
0.01-4 parts by weight of type A zeolite (Zn)
(b) A stabilized flame-retardant thermoplastic resin composition, characterized in that 0.01-5 parts by weight of a dialkyltin malate polymer or/and dialkyltin malate ester salt is added.