JPH0618959B2 - Method for thermally stabilizing styrene resin composition containing halogen-containing flame retardant - Google Patents

Description

The present invention relates to a method for thermally stabilizing a styrene resin composition containing a halogen-containing compound as a flame retardant.

[Industrial application field]

INDUSTRIAL APPLICABILITY The method of the present invention can be widely used in fields where flame retardancy and impact resistance are required for styrene resins.

[Conventional technology]

Generally, a method of adding a so-called flame retardant or a flame retardant aid such as a halogen-containing compound, a phosphorus compound, antimony trioxide or the like has been conventionally performed for flame-retarding a styrene-based resin. Compounds, especially bromine compounds, are effective.

However, it is generally known that when a halogen-containing flame retardant is added to a styrene-based resin, the thermal stability of the resin composition is significantly reduced. Conventionally, there is a method of adding an organic tin compound, an epoxy compound, a phosphorus compound, an antioxidant, etc., or a metal salt of maleic acid (Japanese Patent Publication No. 56-54023).

[Problems to be Solved by the Invention]

Among the above methods, the method of adding an organic tin compound suppresses the decrease in thermal stability to some extent, but the thermal stabilizing effect is not yet satisfactory, and the development of a stabilizer having a further excellent thermal stabilizing effect is awaited. Was there.

[Means for solving problems]

From this point of view, the present inventors have conducted extensive studies on a stabilizer having an excellent thermal stabilizing effect on a resin composition obtained by adding a halogen-containing flame retardant to a styrene resin, and as a result, the halogen-containing flame retardant was contained. By adding an A-type zeolite represented by the general formula Na ₂ O · Al ₂ O ₃ · 2SiO ₂ · XH ₂ O (X represents a number of 0 to 6) to the styrene resin composition. The inventors applied for a patent, finding that the thermal stability of the resin composition is remarkably improved, but as a result of further research, 100 parts of the styrene resin and 5 to 35 parts of the halogen-containing flame retardant were added to the general formula. The A-type zeolite represented by Na ₂ O.Al ₂ O ₃ .2SiO ₂ .xH ₂ O (wherein x represents a number of 0 to 6) and the barium salt of maleic acid are used in the ratio of 2: 8 to 8: 2. Of 0.025 to 17.5
It was found that the thermal stability of the resin composition is remarkably improved by the addition effect of the addition of these parts in combination, and the present invention has been completed.

The styrene resin used in the present invention is a polymer of vinyl aromatic compound monomer such as styrene and α-methylstyrene, α-substituted styrene, vinyltoluene, nucleus-substituted styrene such as 0-chlorostyrene, and the like. Of these vinyl aromatic compound monomers, other monomers copolymerizable therewith, such as acrylonitrile, acrylic acid and methacrylic acid, vinyl compounds such as their methyl or ethyl esters, vinyl pyridine, vinyl carbazone Copolymers with vinyl heterocyclic compounds, etc., other conjugated diene compounds such as butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and EPD
Examples thereof include a vinyl aromatic compound monomer alone to a saturated rubber such as M and butyl rubber, or a graft polymer obtained by grafting this with a vinyl aromatic compound monomer.

As the halogen-containing flame retardant used in the present invention, those generally used in this field can be used without limitation, and examples thereof include tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, Tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate,
Chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, perchlorpentacyclodecane, brominated polyphenyl, tetrabromoethane, tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, vinyl chloroacetate, bromostyrene, bromophenyl Allyl ether, diallyl chlorendate, het acid, het anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, tetrabromobisphenol A, decabromodiphenyl ether, tris (2,3-dibromopropyl) isocyanurate , Tetrabromobisphenol A carbonate oligomer, bis (tribromophenoxy) ethane, and the like.

The amount of the halogen-containing flame retardant added is not particularly limited, but may be appropriately changed depending on the required degree of flame retardancy, and generally 5 to 35 parts by weight with respect to 100 parts by weight of the styrene resin, or 2 It is preferable to use one or more kinds in combination. Further, when a flame retardant aid such as antimony trioxide is used together, the flame retardant effect is more excellent, and the addition amount thereof is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the styrene resin.

The A-type zeolite used in the present invention includes natural and synthetic A-type zeolite.

The barium salt of maleic acid used in the present invention is a neutral salt,
Examples thereof include acidic salts and basic salts, which can be obtained by reacting maleic acid or maleic anhydride with barium oxide or barium hydroxide as a raw material. The combined addition amount of the A-type zeolite and the barium salt of maleic acid is appropriately determined depending on the kind of the halogen-containing flame retardant used for flame retardation, and is based on 100 parts by weight of the styrene resin. A type zeolite and barium salt of maleic acid in total of 0.025 to 1
It is 7.5 parts by weight.

The combination ratio of the A-type zeolite and the barium salt of maleic acid is not particularly limited, but A-type zeolite: barium salt of maleic acid = 8: 2 to 2: 8 is preferable, and particularly preferable is 5: 5 to 2: 8 If it is out of this combination ratio, the replenishment effect is poor, which is not preferable. When actually blended, the A-type zeolite and the barium salt of maleic acid may be added separately to the styrene-based resin containing a halogen-containing flame retardant, or the A-type zeolite and the barium salt of maleic acid may be mixed in advance. You may add what was done.

In carrying out the present invention, a halogen-containing flame retardant is added to a styrene resin, A-type zeolite and a barium salt of maleic acid are further added, and mixed with a mixer such as a Hensiel mixer or a Banbury mixer. do it.

Alternatively, a mixture of a halogen-containing flame retardant, an A-type zeolite, and a barium salt of maleic acid may be added to the styrene resin and blended.

In addition to the stabilizer of the present invention, if necessary, an organic tin compound, an epoxy compound, an organic phosphite ester, an antioxidant, various metal soaps, flame retardant aids, pigments, fillers, lubricants, foaming agents, etc. It can be added.

[Examples and effects]

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In these examples, parts means parts by weight.

Example 1. Acrylonitrile-butadiene-styrene resin [Nippon Synthetic Rubber Co., Ltd., JSRABS # 10NP] 100 parts, bis (tribromophenoxy) ethane [Great Lakes KK Great Lakes FF-680] 20 parts, chlorinated polyethylene [Showa Eraslen 303B manufactured by Denko K.K., and a mixture obtained by adding the stabilizer shown in Table 1 to 3 parts was kneaded for 5 minutes with an 8-inch test roll adjusted to 130 ° C. to prepare a sheet having a thickness of 0.5 mm. . After cutting the obtained sheets, eight sheets were stacked and pressed at 250 ° C., and the time until the sample turned brown or black was measured.

As can be seen from [Table 1], it can be seen that the combined use of the A-type zeolite used in the present invention and the barium salt of maleic acid is excellent in the heat stabilizing effect.

Sample Nos. 4, 7, and 9 used Tetrabrom Bisphenol A [Teijin Kasei Co., Ltd. Fireguard 2000] instead of Great Lakes FF-680.

Example 2. Styrene resin [Asahi Kasei Co., Ltd., Styron 492] 100
Part, hexabromocyclododecane [Daiichi Kogyo Seiyaku Co., Ltd.
Pyroguard SR-103] (15 parts), antimony trioxide (7 parts), and a stabilizer compound shown in [Table-2] were mixed for 5 minutes with an 8-inch test roll adjusted to 120 ° C to obtain a thickness of 0.7 mm.
The sheet of was produced.

After cutting the obtained sheets, eight sheets were stacked and pressed at 230 ° C., and the time until the sample turned brown or blackened was measured.

As can be seen from [Table 2], it can be seen that the combined use of the A-type zeolite used in the present invention and the barium salt of maleic acid has an excellent heat stabilizing effect.

Continuation of front page (56) Reference JP 61-115948 (JP, A) JP 54-66956 (JP, A) JP 54-34356 (JP, A) JP 57-28145 (JP , A)

Claims (1)

[Claims] To 1. A 100 parts by weight of a styrene resin and halogen-containing flame retardant 5 to 35 parts by weight, of the general formula _{Na 2 O · Al 2 O 3} · 2SiO 2 · xH 2 O ( wherein x is 0 to 6 A) zeolite and barium salt of maleic acid represented by the formula: 0.025 to 17.5 at a ratio of 2: 8 to 8: 2.
A method for thermally stabilizing a styrene-based resin composition containing a halogen-containing flame retardant, characterized by comprising adding parts by weight together.