JPH0819255B2 - Flame retardant composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a flame-retardant composition that produces a small amount of gas harmful to the human body during combustion, and particularly when a flame-retardant composition containing red phosphorus is burned. This is to reduce the harmful phosphine gas generated.

"Prior art" For flame retardant methods of rubber and plastics, halogen-free polymers such as polyethylene and aluminum hydroxide,
Some include a hydrous inorganic filler such as magnesium hydroxide. Although this one has the feature that it does not generate harmful and corrosive hydrogen halide gas at the time of combustion, sufficient flame retardancy cannot be obtained unless a large amount of water-containing inorganic filler is added,
When a large amount of a water-containing inorganic filler is blended, there is a drawback that mechanical properties such as elongation of the composition are significantly reduced.

As a method for improving such a drawback, a method has been proposed in which red phosphorus or a flame retardant containing red phosphorus is used in combination with a hydrous inorganic filler to reduce the content of the hydrous inorganic filler.

"Problems to be solved by the invention" However, in a composition in which the flame retardant containing red phosphorus or red phosphorus is used in combination with a water-containing inorganic filler, the composition thereof is burned, especially when burned in an oxygen-deficient state. Had a problem of generating extremely harmful phosphine gas.

[Means for Solving Problems] In the present invention, a halogen-free rubber or plastic is added to a water-containing inorganic filler, red phosphorus, and an organic solvent having a decomposition temperature of 130 ° C. or more to obtain a half-life of 10 hours. By adding an oxide, generation of phosphine gas during combustion was prevented.

 The present invention will be described in detail below.

A halogen-free rubber used in the present invention,
As plastic, silicone rubber, butyl rubber,
Natural rubber, rubber such as styrene-butadiene rubber, butadiene rubber, nitrile rubber, polyethylene, polypropylene, ethylene propylene rubber, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polyamide, polyethylene terephthalate, polycarbonate, Thermoplastic resins such as polyacrylic acid esters are used, and blends thereof are also used.

Further, as the water-containing inorganic filler, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), kaolin clay (Al _{2
O 3 · 2SiO 2 · 2H 2} O), diatomaceous earth _{(SiO 2 · nH 2 O)} , talc _{(3MgO · 4SiO 2 · H 2} O), mica _{(K 2 O · 3Al 2 O} 3 · 6SiO 2
・ 2H ₂ O), wax stone clay (Al ₂ O ₃・ 4SiO ₂・ H ₂ O), hemihydrate stone (CaSO ₄ ; 0.5H ₂ O), dihydrate stone (CaSO ₄・ 2H ₂ O)
A metal oxide having crystal water such as is used.

Furthermore, the decomposition temperature for obtaining a half-life of 10 hours is 130
As organic peroxides having a temperature of ℃ or higher, p-menthane hydroperoxide (decomposition temperature 133 ℃ to obtain a half-life of 10 hours), 2,5-dimethyl-2,5 di (t-butylperoxy) Hexane-3 (same decomposition temperature 135 ℃), 1,1,3,3-
Tetramethylbutyl hydroperoxide (decomposition temperature 153 ° C), 2,5-dimethylhexane-2,5-dihydroperoxide (decomposition temperature 154 ° C), cumene hydroperoxide (decomposition temperature 158 ° C), t -Butyl hydroperoxide (at the same decomposition temperature of 167 ° C) is used. The decomposition temperature for obtaining a half-life of 10 hours means the decomposition temperature for reducing the amount of active oxygen in the organic peroxide to 1/2 in 10 hours.

And these compounding agents are rubber containing no halogen,
50-200 hydrated inorganic filler for 100 parts by weight of plastic
Parts by weight, 1 to 10 parts by weight of red phosphorus, and 1 to 10 parts by weight of an organic peroxide having a decomposition temperature of 130 ° C. or higher for obtaining a half-life of 10 hours. The addition amount of the water-containing inorganic filler is mainly determined by the flame retardancy required for the flame retardant composition,
If it exceeds 200 parts by weight, the mechanical properties of the flame-retardant composition will be significantly deteriorated and it will be impractical, and if it is less than 50 parts by weight, sufficient flame retardancy will not be obtained. Further, red phosphorus further enhances the flame retardancy of the composition, and by adding it, the compounding amount of the hydrated inorganic filler can be reduced, and it is also determined according to the degree of flame retardancy required, and 1% by weight. If it is less than 10 parts by weight, the effect of addition cannot be obtained, and if it exceeds 10 parts by weight, the mechanical properties of the composition are largely deteriorated, and the amount of phosphine gas generated is large, which is disadvantageous. Further, if the amount of the organic peroxide is less than 1 part by weight, the effect of suppressing the generation of phosphine gas cannot be obtained, and if it exceeds 10 parts by weight, the compatibility becomes poor, which is disadvantageous.

To such a flame-retardant composition, if necessary, a colorant, other filler such as calcium carbonate, a plasticizer, a stabilizer, a compounding agent such as an ultraviolet absorber can be added, and 10 Decomposition temperature is 130 ℃ to obtain half-life of time
Less than dicumyl peroxide (same decomposition temperature 117 ℃),
t-Butyl cumyl peroxide (same decomposition temperature 120 ℃)
Addition of low-temperature decomposable organic peroxides such as, and low-temperature activated cross-linking agents such as ionic cross-linking agents (vulcanizing agents) to obtain a half-life of 10 hours. It is also possible to promote the effect of suppressing the generation of phosphine gas by the substance. In this case, the addition amount of the low temperature active cross-linking agent is 1 to 10 with respect to 100 parts by weight of rubber and plastic that do not contain halogen.
It is about part by weight.

Such flame-retardant composition, after being mixed and kneaded by a mixer such as a rotary mixer, a ribbon blender, a high-speed mixer or a kneader such as an intensive mixer or a kneader, an extrusion molding machine, an injection molding machine, etc. It is molded into a desired shape and used as an electric wire coating, electrical equipment parts, building material, disaster prevention material, and the like.

The flame-retardant composition having such a composition exhibits a high degree of flame retardancy and suppresses the generation of phosphine gas due to red phosphorus during combustion. In a composition containing red phosphorus, red phosphorus is reduced and phosphine gas is generated when the composition is in an oxygen deficient state during combustion. At this time, if the organic peroxide is blended, the organic peroxide is decomposed during combustion, and the oxidation reaction thereof prevents the reduction of red phosphorus and suppresses the generation of phosphine gas. Since a high-temperature activated organic peroxide having a decomposition temperature of 130 ° C. or higher is selected here, this organic peroxide hardly decomposes during kneading or molding, and most of the organic peroxide does not decompose after molding. Also remains and decomposes for the first time during combustion, effectively suppressing the red phosphorus reduction reaction. Further, the amount of carbon monoxide gas generated during combustion also decreases due to the promotion of the oxidation reaction.

"Experimental Example" A composition having a composition shown in Table 1 was extruded to obtain a plate-shaped test piece having a thickness of 2 mm. For this, while determining the oxygen index by the oxygen index method according to JIS-K7201, measure the content of hydrogen halide, carbon monoxide, carbon dioxide, phosphine gas in the generated combustion gas, also at the time of fracture of the test piece The elongation was measured. The results are shown in Table 1.

Further, for comparison, the composition having the composition shown in Table 2 was extrusion-molded to prepare a similar plate-shaped test piece, and the same measurement was performed for this. The results are shown in Table 2.

As is clear from the results shown in Tables 1 and 2, the composition according to the present invention exhibits high flame retardancy, excellent mechanical properties (elongation), and the amount of phosphine generated is significantly reduced.
It can be seen that the amount of carbon monoxide generated is also reduced.

"Effects of the Invention" As described above, the flame-retardant composition of the present invention has a halogen-free rubber and a plastic, a hydrous inorganic filler and red phosphorus, and a decomposition temperature for obtaining a half-life of 10 hours. 130
Since the organic peroxide having a temperature of not less than 0 ° C. is added, the generation of phosphine gas due to the addition of red phosphorus is suppressed and the flame retardancy is high.

Claims (1)

[Claims] 1. A rubber or plastic containing no halogen,
A flame-retardant composition comprising a water-containing inorganic filler, red phosphorus, and an organic peroxide having a decomposition temperature of 130 ° C. or higher for obtaining a half-life of 10 hours.