CN1009275B

CN1009275B - Flame-retardant composition and flame-retardant cable using the same

Info

Publication number: CN1009275B
Application number: CN 85101465
Authority: CN
Inventors: 长谷川正毅; 小林弘忠; 砂塚英夫; 吉野明; 松田隆夫; 新乡善興
Original assignee: Fujikura Ltd
Current assignee: Fujikura Ltd
Priority date: 1984-08-14
Filing date: 1985-04-01
Publication date: 1990-08-22
Also published as: CN85101465A

Abstract

The flame retardant composition was formulated as follows: 100 parts by weight of the halogen-free rubber or plastic is mixed with about 50 to 200 parts by weight of magnesium hydroxide having an average particle size of about 0.3 to 2 μm and about 5 to 50 parts by weight of carbon black powder having an oil absorption capacity of about 0.5 to 2.0ml/g, and the mixture is crosslinked with an organic peroxide, sulfur or a sulfide as a vulcanizing agent. The composition and the flame-retardant cable using the composition as an insulating layer and/or a sheath comprise a plurality of cable cores which are wrapped by insulating layers or twisted together by using fillers and wrapped by the sheath, have excellent flame-retardant and mechanical properties, have less smoke in case of fire, do not emit hydrogen halide or other toxic gases, and have small harmfulness.

Description

Fire retardant composition and cable made from same

The invention relates to the halogen-free flame-retardance composition, and the flame retardant resistance cable that uses said composition to make.

The fire-retardant method of common cable has three kinds:

(1) adopts by the high flame-retardant resin that contains halogen such as chlorine or bromine (as polyvinyl chloride (PVC), chloroprene rubber, chlorosulfonated polyethylene (Hai Pulong) rubber or chlorinatedpolyethylene) or be added with cable insulation or the crust that the similar resin of weisspiessglanz or other similar fire retardant is made in order to improve flame retardant resistance.

(2) use by flammable resin (as polyethylene, ethene-vinyl acetate copolymer (EVA), ethylene-acrylic acid second fat (EEA), or ethylene-propylene rubber(EPR) (EPR)) and contain halogen such as chlorine or bromine and add insulation layer and the crust that the fire retardant of weisspiessglanz is made.

(3) use aluminium hydroxide to replace halogen containing flame-retardant to be added in the flammable resin as main fire retardant.

In method (1) and (2), the insulation layer of cable and crust attach or do not attach fire retardant by a kind of Halogen resin and make.Like this, when the burning of resin and fire retardant or produced in other cases (a large amount of halogenation hydrogen of (HCl) or hydrogen bromide (HBr) class can corroding metals, harmful to human such as hydrogenchloride.The dense smoke that produces during burning also is the difficult problem of a bad solution.In sum, these flame-retardant compositions and be not harmless article with the cable that these compositions are made.Therefore, these article can not be used for subway, market place builet below the ground, hospital, office building, boats and ships, Nuclear power plants, chemical plant and some other facility very relevant with personnel safety.

Last a kind of method (8) is to use aluminium hydroxide to be added in the flammable resin as main fire retardant.This method is different with (2) with method (1), and it can not distribute toxic gas and dense smoke.But, want to improve fire retardancy, just must increase the ratio of lead hydroxide in composition.The flame retardant cable crust that will reduce this flame-retardant composition itself like this or make by said composition or the mechanical property of insulation layer and (or) electric property.Another shortcoming of method (3) is that this composition may produce useless foam in the courses of processing such as extruding.

The present invention is intended to solve the problems referred to above that exist in the common process.Flame-retardant composition is a content of this invention.Its compound method is to sneak into earlier about 50 to 200 parts of average particulate diameters to be about the carbon black powder that 0.3 to 2 micron magnesium hydroxide and about 5 to 50 parts of oil absorptions are about 0.5 to 2.0 milliliter/gram in 100 parts of (following all calculate by weight) halide-free rubbers or plastics, and the organo-peroxide, sulphur or the sulfide that are used as vulcanizing agent then make this mixture crosslinked.

Another content of this invention is a flame retardant cable.It comprises the uniconductor only son and heir cable core that is covered with insulation layer, or several similar cable core that is screwed in together and is covered by crust together with filler.Above-mentioned insulation layer and (or) crust made by a kind of flame-retardant composition.The compound method of this flame-retardant composition is: in 100 parts of (following all calculations by weight) halide-free rubbers or plastics, sneak into about 50 to 200 parts of average particulate diameters and be about the carbon black powder that 0.3 to 2 micron magnesium hydroxide and about 5 to 50 parts of oil absorptions are about 0.5 to 2.0 milliliter/gram, be used as the organo-peroxide of vulcanizing agent then, sulphur or sulfide make this mixture crosslinked.

As mentioned above, flame-retardant composition manufactured according to the present invention and have stronger fire resistance property with the flame retardant resistance cable that this flame-retardant composition is made, and, be Halogen by the composition itself of forming as the halide-free rubber of unmodified resin or plastics and Halogen additive.Therefore, this cable can not discharge any hydrogen halide or other toxic gas in fire or during the burning of other inflammable place.Contiguous metal is neither corroded in the combustion gas that the burning cable produces, and does not also injure human body.Because the smog that produces during this cable fire is few than normal cable, therefore, inflammable local use safer.Its another advantage is a good mechanical property.

Fig. 1 and Fig. 2 are the cross section with the made flame retardant cable of flame-retardant composition.This is as embodiments of the invention.

The rubber that uses among the present invention and plastics are Halogens, this class material has polyethylene (PE), natural rubber, butyl rubber, silicon (oxygen) rubber, EPM (EPR), tri poly ethylene-propylene rubber (EPDM), ethene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethene-alpha-olefin copolymer, ethylene-acrylic rubber, HSBR, lactoprene and their mixture thereof. In order to obtain higher tensile strength and other good mechanical performance, should use the polyene resin that has at least 90% ethene composition or the compound that uses two or more polyene resin.

The regulation according to the present invention, the average particulate diameter of contained magnesium hydroxide is about 0.3 to 2 micron in the flame-retardant composition. Particle diameter has very big cohesive force less than 0.3 micron magnesium hydroxide, can not thoroughly disperse when mixed, and mechanical performance and other performance of prepared composition produced harmful effect. Particle diameter also is worthless greater than 2 microns magnesium hydroxide, because the total surface area of this particle reduces, thus the mechanical performances such as the tensile strength of reduction composition and percentage elongation. During magnesium hydroxide in use is crushed to the given size scope, although the mechanical performance of prepared composition and extrudability are slightly influenced, can obtain stronger filling capability, and the enhancing of filling capability will produce good fire resistance. Regulation is calculated by weight according to the present invention, should add about 50 to 200 parts of magnesium hydroxides in per 100 parts of rubber or the plastics. If magnesium hydroxide is less than 50 parts (calculating by weight), just can not reach good flame retardant effect. But surpass 200 parts, magnesium hydroxide will be too much, thereby reduce the mechanical performance of composition, and produce foam or become when extruding and be difficult to processing. With regard to magnesium hydroxide, discharge the temperature of the crystallization water about 370 ℃, or be higher than the temperature (about 200 ℃, this temperature will be lower than the treatment temperature of some resin, and is therefore, restricted to selecting resin) of aluminium hydroxide. Because crystallization water release temperature is very high, very near the thermal decomposition point of primary resin, therefore, in fact all be not unrestricted to the temperature of magnesium hydroxide and mixed with resin and to the extrusion temperature of prepared composition. With stearic acid or oleic acid the filling capability that can greatly improve composition is processed on the magnesium hydroxide surface, can also be improved its processing characteristics simultaneously.

Stipulate that by the present invention the oil absorption of used carbon black is about 0.5 to 2.0 milliliter/gram, this makes the existing good flame retardant effect of composition, and good processing characteristics and mechanical performance are arranged again. When oil absorption less than 0.5 milliliter/when gram because the surface of carbon black gross area is limited, tensile strength will reduce, flame retardant effect will variation. If oil absorption surpasses 2.0 milliliters/gram, the viscosity of mixture will be excessive and can't process, and the insulating properties of composition also can descend.

By the present invention's regulation, calculate by weight, should add about 5 to 50 parts of carbon blacks in per 100 parts of rubber or the plastics.When carbon black is less than 5 parts, (calculate by weight), just can not produce needed fire-retardant and carburization zone formation effect; But when carbon black surpasses 50 parts (calculating by weight), mixture viscosity can not be processed too greatly, or reduces the product unit elongation.When flame-retardant composition caught fire, contained carbon black was heated under anaerobic state, and in carbonization process, formed a carburization zone in composition.The carburization zone of Xing Chenging has prevented flowing of composition itself effectively like this, can also prevent combustiblesubstance (fusing drip) simultaneously from the inner outflow of cable, thereby control spreading of the intensity of a fire.

The vulcanizing agent that regulation of the present invention is used has superoxide, dicumyl peroxide (DCP), 2,5-dimethyl-2,5-two (t-butyl peroxy alkynes) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin and tertiary butyl peroxybenzoic acid salt.Other available vulcanizing agent has the compound of sulphur, sulphur and thiuram vulcanizing agent.According to the present invention made flame-retardant composition and this class vulcanizing agent crosslinked after, show excellent mechanical property.

Using when of the present invention, be preferably in the red phosphorus that adds about 2 to 15 parts (calculating by weight) in the rubber of 100 parts (calculating by weight) and the plastics.If in fact the quantity of red phosphorus do not have the effect of accelerated carbonation less than 2 parts (calculating by weight).Otherwise,, can reduce flame retardant resistance, and distribute more smog if the red phosphorus dosage surpasses 15 parts (calculating by weight).The red phosphorus that surpasses specified quantity also can promote the carbonization of flame-retardant composition inside to cause burning.This is because when heating up, red phosphorus is subjected to thermooxidizing, must make resin lose hydrogen, and makes resin pass through dehydration reaction and carbonization.As long as a spot of red phosphorus is arranged, preferably combine, just dehydration and carbonization can take place with above-mentioned magnesium hydroxide.When making the unmodified resin fire retardant, use material of the presently claimed invention, i.e. the magnesium hydroxide that granular size is certain, carbon black and red phosphorus with certain oil absorption.That the smog that discharges during this composition burn is less than is chloride, the common fire retardant of bromine or other halogen.

Be preferably in the said mixture, calculate by weight and add about 3 parts to 10 parts organopolysiloxane respectively in per 100 parts of rubber or the plastics and molecular formula is xPbOPb(R) yH ₂The alkali formula leadization thing of O.0≤X in the formula≤3; R is sulfate radical, higher fatty acid acid group or aromatic carboxylic acid root (higher fatty acid acid group and aromatic carboxylic acid root respectively have the carbon atom more than six or six); 0≤y≤10.Organopolysiloxane comprises as dimethyl polysiloxane, methylbenzene polysiloxane and methylvinyl-polysiloxane.Alkalescence leadization thing can be tribasic lead sulfate, dibasic lead phthalate or alkali formula lead stearate.Organopolysiloxane of adding and alkali formula leadization thing respectively are less than three parts just can not improve fire retardancy effectively.On the other hand, these two kinds of additives all surpass 10 parts, or the blending ratio of these two kinds of additives too metropolitan reduce the tensile strength of composition.The ratio that increases your additive differs and improves flame retardant resistance surely significantly, sees also originally and there is no need from producing.

Introduce the flame retardant cable made from above-mentioned flame-retardant composition by the present invention referring now to Fig. 1.Reference number 1 expression electric conductor among the figure, its outside is wrapped in by the insulation layer 2 that routine is crushed to by one deck entirely, forms sub-heart yearn 3.Insulation layer 2 is by flame-retardant composition, or made by a kind of halide-free rubber or plastics.The three strip heart yearns of making according to the method described above are screwed in together, with filler 4(such as paper tape, jute or congener) composition heart yearn 5.The outside of heart yearn 5 is crusts 6, and it has used flame-retardant composition of the present invention and has made by common pressing method.

Fig. 2 is another embodiment with the made flame retardant cable of flame-retardant composition of the present invention.The label of cable element is identical with label among Fig. 1 among the figure, therefore, just no longer repeats here.At this structural modification flame retardant cable in, increase on every strip heart yearn 3 and wrapped up in one deck heart yearn band 7, be the band of " Mylar(polyester film) " as selling trade mark.These three the sub-heart yearns that are wrapped with heart yearn band 7 are screwed in together, are pressed with filler 8 in the sub-heart yearn outside of kinking.Filler 8 is solid-state, is at least 30 halogen-free flame-retardance composition by oxygen index and makes.Using this kind solid fillers place, be preferably in sub-heart yearn 3 outsides and wrap one deck Mylar(polyester film) or similar heart yearn band 7, to prevent fusion between filler and the heart yearn.Equally, wrap up in one deck Mylar(polyester film in the outside of solid fillers 8) or similar fixing strip.But, this fixing strip 9 not right and wrong with can not.Be at least the filler that 30 halogen-free flame-retardance composition makes and be used for above-mentioned cable by containing oxygen index, the crust made from flame-retardant composition of the present invention and (or) insulation layer combines, and will make cable have bigger flame retardant resistance.

Although what the present invention introduced is a kind of many conductors type cable, it is not limited to this a kind of cable, and it also is applicable to uniconductor type cable.

Embodiment 1～10 and comparative example 1～10

Table 1 is the table look-up of embodiment 1～10, and it can be used for preparing flame-retardant composition according to the present invention, and composition and the performance test result of each embodiment is provided.Table 2 has been summed up as a comparative example the composition of 1～10 the non-scope of the invention and the composition and the performance test result of common polychloroethylene composition.In table 1 and table 2, all samples except that comparative example 6 and 7 all is at 110 ℃ of following use roller crushers that composition is mixed, crosslinked for 30 minutes 160 ℃ of following hot pressing then, forms the thin plate that thickness is 2mm at last.

As can be seen from Table 1, in embodiment 1～10, the flame-retardant composition that belongs to the present invention's row all has good machinery, processes, is fuming and flame retardant properties.

On the other hand, table 2 has disclosed the following fact: in comparative example 1, the ratio of magnesium hydroxide is too little, and the composition of making is not enough to fire-retardant, thereby can burn in air.In contrast, in comparative example 2, magnesium hydroxide is too many, thereby the processing characteristics of composition and unit elongation are descended.In the 3rd embodiment, carbon black is excessive, has also influenced processing characteristics and unit elongation.What comparative example 4 used is the carbon black of a kind of oil absorption low (0.4 milliliter/gram), and the result has reduced tensile strength and flame retardant properties.Comparative example 5 has used excessive red phosphorus (red phosphorus content is calculated by weight and accounted for 17%), and the result is identical with last example.Comparative example 6 and 7 uses conventional chloride composition (be flame retarding polyvinyl chloride (PVC) composite and contain the lower flame retarding polyvinyl chloride (PVC) composite of HCl), and as crust, its prescription is shown in table 2A.This composition is at oxygen index (O ₁) and the tensile strength aspect made balance, but it can disperse smog, especially disperses hydrogen halide.In view of these two kinds of compositions have corrodibility and toxicity, so be not satisfactory.

Table 2A

Comparative example is (with heavy

Amount is calculated

Mark)

6 7

Polyvinyl chloride (PVC) resin (p=1100) 100 100

(dioctyl phthalate (DOP)) softening agent 50 60

（DOP）

Stablizer (dilaurylformamide) 44

（DLF）

Sb ₂O ₃10 10

CaCo ₃- 50

Comparative example 8 uses a kind of carbon with higher oil absorption as raw material, and (Mooney viscosity) is very high for the composition mooney viscosity of making, so poor processability.The less Mg(OH of comparative example 9 usefulness average particulate diameters) ₂As raw material, the result is that the unit elongation of composition is little, poor processability.Comparative example 10 has adopted the Mg(OH of macrobead diameter) ₂(magnesium hydroxide) as raw material, the tensile strength of its composition and unit elongation are relatively poor as a result.

Embodiment 11～14 and comparative example 11～15

The sample of the listed composition of table 3 and table 4 is to prepare by the distribution of the foregoing description.

As shown in table 3, the flame-retardant composition of preparation all has good machinery, processes, is fuming and flame retardant properties according to the present invention.

Table 4 has disclosed the following fact: in comparative example 11, the combined amount of organopolysiloxane and leadization thing is excessive, and the composition tensile strength of making weakens, the fire retardancy deficiency.Comparative example 12 uses brominated flame-retardants, and (composition made of+bromine phenylbenzene oxidation thing (decabromodiphenyl oxide) is dispersed a large amount of bromize hydrogen gas and smog.Comparative example 13 and 14 makes conventional chloride composition as cable sheath (be flame retarding polyvinyl chloride (PVC) composite and contain the lower flame retarding polyvinyl chloride (PVC) composite of HCl) respectively, and these compositions composition with table 2A comparative example 6 and 7 respectively are identical.These two kinds of samples have equilibrated oxygen index and tensile strength, but will disperse macro-corrosion and toxic hydrogen halide and smog.Comparative example 15 has used a small amount of organopolysiloxane and three alkali lead sulfates, and its result makes the flame retardant properties variation of composition.

Embodiment 15～19 and comparative example 16～21

Table 5 has been summed up the flame retardant cable of making according in the embodiment of the invention 15～19, and structure and performance test result.Table 6 is introduced as a comparative example non-the present invention of usefulness of 16～21 the composition and the structure and the performance test result of the made cable of common polychloroethylene composition.Each sample cable is all by making with figure similar methods illustrated in figures 1 and 2.

Can be clear that from table 5 flame retardant cable of making according to the present invention regulation all meets " Institute of Electrical and Electronics Engineers standard 383(IEEE Std.383) ".Cable surface processing is attractive in appearance, does not disperse hydrogen chloride gas, has only light weight smog, has 100 meters visibility meter in all cases at least.The result shows is needing the higher place of fire retardancy preferably to use solid-state fire-retardant filler.

Table 6 shows that by contrast it is worthless using the cable of the low oxygen index crust in the comparative example 16 and 17.Even have oxygen index in the comparative example 17 and be 26 insulation layer, this cable also is underproof.The cable of comparative example 18 has passed through combustion test, but filler is many, has influenced processing characteristics, surface irregularity in addition, and outward appearance is indecency and become substandard products.Comparative example 19 to 21 all uses the polyvinyl chloride crust.Although these several cables have passed through combustion test, when on fire, produce a large amount of hydrogen chloride gas, corroding metal, the injury human body is also dispersed a large amount of smog simultaneously.

Embodiment 20～22 and comparative example 22～25

Table 7 has been introduced the cable and the The performance test results thereof of producing according to the embodiment of the invention 20 to 22.Equally, table 8 has been introduced as a comparative example the composition of 22～25 the non-scope of the invention of usefulness and cable and performance test result thereof that the common polythene cable composition is made.Every sample cable all adopts and embodiment 11～14 and comparative example 11～15 similar methods.

Table 1

Embodiment

1 2 3 4 5

Composition composition (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}100 100 100 100 100

Magnesium hydroxide ^{* 2}---100 150

Surface treated magnesium hydroxide ^{* 3}50 100 150--

Carbon black ^{* 4}50 20 20 20 20

Contain red phosphorus combustion inhibitor ^{* 5}-----

Antioxidant ^{* 6}22222

Dicumyl peroxide 22222

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}1.6 1.4 1.2 1.2 1.0

Unit elongation (%) ^{* 7}570 520 470 420 370

Oxygen index ^{* 8}26 28 33 26 33

Hydrogen halide (milligram/gram) ^{* 9}00000

The bronze mirror corrosion test

Corroded area (%) ^{* 10}00000

Temperature is at 100 ℃ mooney viscosity ^{* 11}40 25 30 42 57

Disperse smog, D(m ^-1) ^{* 12}0.7 0.6 0.5 0.6 0.5

Annotate:

^*1 contains the polyene resin of 90% ethene at least, is sold by Japanese Mitsui petrochemical complex Industrial Co., Ltd, and its trade mark is " TAFUMER A-4085 ".

^*2 not surface treated magnesium hydroxides, average particulate diameter is 2 microns.

^*The surface-treated magnesium hydroxide of 3 usefulness stearic acid, average particulate diameter is 0.3 micron.

^*The oil absorption of 4 this kind carbon black structures be 1.2 milliliters/gram (high abrasion furnace black(HAF)) (HAF).

^*5 contain 24%(calculates by weight) fire retardant of red phosphorus.

^*6 Switzerland Chiba-Geigy companies produce and sell, and trade mark is " Irganex#1076 ".

^*7 according to ASTM D-638.

^*8 according to ASTM D-2863.

^*9 according to IEC 754-1.

^*10 according to ASTM D-2671.

^*11 ML ₁₊₄Minimum value.

^*12 measure according to the JIS A-1306 of Japanese Industrial Standards.Smokescope D=1/Llog ₁₀I ₀/ I, in the formula, L is path length (rice); I has cigarette light intensity, I ₀It is smokeless light intensity.

Table 1(is continuous)

Embodiment

6 7 8 9 10

Composition composition (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}100 100 100 100 100

Magnesium hydroxide ^{* 2}-----

Surface treated magnesium hydroxide ^{* 3}200 100 100 100 150

Carbon black ^{* 13}5 20 20 20 20

Contain red phosphorus combustion inhibitor ^{* 5}-10 30--

Antioxidant ^{* 6}22222

Dicumyl peroxide 22222

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}1.0 1.2 1.0 1.6 1.0

Unit elongation (%) ^{* 7}360 510 480 520 500

Oxygen index ^{* 8}39 30 35 29 27

Hydrogen halide (milligram/gram) ^{* 9}00000

The bronze mirror corrosion test

Corroded area (%) ^{* 10}00000

Temperature is at 100 ℃ mooney viscosity ^{* 11}45 24 26 30 25

Disperse smog, D(m ^-1) ^{* 12}0.4 0.8 0.9 0.6 0.5

Annotate:

^*1～3 He ^*5～ ^*12 is identical with table 1.

^*The oil absorption of 13 these carbon black structures: embodiment 6～8 be 1.2 milliliters/gram (high abrasion furnace black(HAF)) (HAF), embodiment 9 be 2.0 milliliters/gram (fine intermediate super abrasion furnace black high structure) (ISAF-HS), embodiment 10 be 0.5 milliliter/gram (FF fine furnace black).

Table 2

Comparative example

1 2 3 4 5

Composition composition (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}100 100 100 100 100

Surface treated magnesium hydroxide ^{* 3}30 250 100 100 100

Carbon black ^{* 13}3 10 70 20 20

Contain red phosphorus combustion inhibitor ^{* 5}----70

Antioxidant ^{* 6}22222

Dicumyl peroxide 22222

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}1.8 0.6 0.8 0.8 0.7

Unit elongation (%) ^{* 7}620 190 230 570 320

Oxygen index ^{* 8}21 43 30 24 30

Hydrogen halide (milligram/gram) ^{* 9}00000

The bronze mirror corrosion test

Corroded area (%) ^{* 10}00000

Temperature is at 100 ℃ mooney viscosity ^{* 11}20 71 64 23 52

Disperse smog, D(m ^-1) ^{* 12}1.6 0.3 0.5 0.5 2.1

Annotate:

^*1, ^*3, ^*5～ ^*12 is identical with table 1.

^*13 this kind carbon black structure oil absorptions: comparative example 1～3 and 5 be 1.2 milliliters/gram (high abrasion furnace black(HAF)) (HAF), comparative example 4 be 0.4 milliliter/gram (fine particle hot tearing furnace black) (FT).

Table 2(is continuous)

Comparative example

6 7 8 9 10

Composition components (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}--100 100 100

Surface treated magnesium hydroxide ^{* 14}--150 100 100

Carbon black ^{* 15}--40 20 20

Contain red phosphorus combustion inhibitor ^{* 5}-----

Antioxidant ^{* 6}--2 22

Dicumyl peroxide--222

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}2.5 1.6 1.8 1.2 0.7

Unit elongation (%) ^{* 7}300 360 450 220 280

Oxygen index ^{* 8}35 30 35 30 25

Hydrogen halide (milligram/gram) ^{* 9}270 80 000

The bronze mirror corrosion test

Corroded area (%) ^{* 10}100 21 000

Temperature is at 100 ℃ mooney viscosity ^{* 11}--75 82 48

Disperse smog, D(m ^-1) ^{* 12}2.6 2.0 0.7 0.6 0.9

Annotate: ^*1, ^*2, ^*5～ ^*12 is identical with table 1.

^*The average particulate diameter of the magnesium hydroxide that 14 usefulness stearic acid are surface-treated: comparative example 8 is 0.3 micron, and comparative example 9 is 0.2 micron, and comparative example 10 is 3 microns.

^*The oil absorption of 15 these carbon black structures: comparative example 9 and 10 be 1.2 milliliters/gram (high abrasion furnace black(HAF)) (HAF); Comparative example 8 be 2.5 milliliters/gram (high electric conductivity furnace black) (ECF).

Table 3

Embodiment

11 12 13 14

Composition composition (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}100 100 100 100

Magnesium hydroxide ^{* 2}----

Surface treated magnesium hydroxide ^{* 3}100 100 100 100

Carbon black ^{* 4}20 20 20 20

Contain red phosphorus combustion inhibitor ^{* 5}--30 30

Organopolysiloxane ^{* 16}355 10

Three alkali lead sulfates 3-5 10

Binary O-phthalic lead plumbate-5--

Antioxidant ^{* 6}2222

Dicumyl peroxide 2222

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}1.3 1.3 1.0 1.0

Unit elongation (%) ^{* 7}500 505 480 420

Oxygen index ^{* 8}36 37 43 45

Hydrogen halide (milligram/gram) ^{* 9}0000

The bronze mirror corrosion test

Corroded area (%) ^{* 10}0000

Temperature is at 100 ℃ mooney viscosity ^{* 11}23 23 28 35

Disperse smog, D(m ^-1) ^{* 12}0.5 0.5 0.7 0.6

Annotate: ^*1～ ^*12 is identical with table 1.

^*16 dimethyl polysiloxanes.

Table 4

Comparative example

11 12 13 14 15

Composition composition (calculating by weight umber)

Ethene-alpha-olefin copolymer ^{* 1}100 100--100

Surface treated magnesium hydroxide ^{* 3}100---100

Carbon black ^{* 4}20 20---

Organopolysiloxane ^{* 16}20---2

Three alkali lead sulfates 20 5--2

The decabrominated dipheny oxide compound ^{* 17}-40---

Weisspiessglanz (Sb ₂O ₃)-20---

Antioxidant ^{* 6}2 2--2

Dicumyl peroxide 2 2--2

Performance test result

Tensile strength (kilogram/millimeter ²) ^{* 7}0.6 1.5 2.5 1.6 1.3

Unit elongation (%) ^{* 7}420 370 300 360 470

Oxygen index ^{* 8}35 26 35 30 24

Hydrogen halide (milligram/gram) ^{* 9}0 60 270 80 0

The bronze mirror corrosion test

Corroded area (%) ^{* 10}0 15 100 21 0

Temperature is at 100 ℃ mooney viscosity ^{* 11}26 22--23

Disperse smog, D(m ^-1) ^{* 12}0.6 2.8 2.5 2.2 0.7

Annotate: ^*1, ^*3, ^*4 Hes ^*6～ ^*12 is identical with table 1.

^*16 is identical with table 3.

^*17, a kind of fire retardant that contains 83% bromine (calculating by weight).

Claims

1, a kind of flame-retardant composition, it is characterized in that, its compound method is: calculate by weight, in 100 parts of halide-free rubbers or plastics, sneak into about 50 to 200 parts of average particulate diameters and be about the carbon black powder that 0.3 to 2 micron magnesium hydroxide and about 5 to 50 parts of oil absorptions are about 0.5 to 2.0 milliliter/gram, use organo-peroxide, sulphur or sulfide as vulcanizing agent that said mixture is crosslinked then, wherein to contain 3 to 10 parts organopolysiloxane and the molecular formula of having an appointment respectively be xPbO.Pb (R) yH to mixture ₂The alkali formula leadization thing of O, in the molecular formula, 0≤x≤3, R is the higher fatty acid root, aromatic carboxylic acid root, or sulfate radical, higher fatty acid root and aromatic carboxylic acid root all contain the carbon atom more than 6 or 6,0≤y≤10.

2, according to the described flame-retardant composition of claim 1, it is characterized in that, comprised the fire retardant that contains red phosphorus, calculate by weight, sneak into about 2 to 15 parts of red phosphorus in per 100 parts of rubber or the plastics.

According to claim 1 or 2 described flame-retardant compositions, it is characterized in that 3, magnesium hydroxide is to carry out surface-treated with stearic acid or oleic acid.

4, cable core is by the single conductor of tape insulation layer or the flame retardant resistance cable that is screwed in together and is made up of several conductors of crust parcel with filler, it is characterized in that, insulation layer and (or) crust made by a kind of flame-retardant composition, the prescription of this composition is as follows: calculate by weight, in 100 parts of halide-free rubbers or plastics, sneak into about 50 to 200 parts of average particulate diameters and be about 0.3 to 2 micron magnesium hydroxide, and about 5 to 50 parts of oil absorptions are about the carbon black powder of 0.5 to 2.0 milliliter/gram, and then use organo-peroxide, sulphur or sulfide carry out crosslinked to said mixture as vulcanizing agent, wherein mixture to contain 3 to 10 parts organopolysiloxane and the molecular formula of having an appointment respectively be xPbO.Pb(R) yH ₂The alkali formula leadization thing of O, 0≤x in the molecular formula≤3, R is the higher fatty acid root, aromatic carboxylic acid root, or sulfate radical, higher fatty acid root and aromatic carboxylic acid root all contain the carbon atom more than 6 or 6,0≤y≤10.

5, flame retardant resistance cable according to claim 4 is characterized in that, fills out filler between heart yearn or twisting heart yearn and crust and is at least 30 halogen-free flame-retardance composition by oxygen index and forms.

6, according to the described flame retardant resistance cable of claim 4, it is characterized in that it also is added with the fire retardant that contains red phosphorus, calculates by weight, per 100 parts of rubber or plastics are sneaked into about 2 to 15 parts of red phosphorus.

7, flame retardant resistance cable according to claim 6 is characterized in that, fills out filler between heart yearn or twisting heart yearn and the crust and is at least 30 halogen-free flame-retardance composition by oxygen index and forms.

8, according to claim 4 or 6 described flame retardant resistance cables, it is characterized in that, fill out filler between heart yearn or twisting heart yearn and crust and be at least 30 halogen-free flame-retardance composition by oxygen index and form.

According to claim 4 or 5 described flame retardant resistance cables, it is characterized in that 9, magnesium hydroxide is to carry out surface-treated with stearic acid or oleic acid.

10, flame retardant resistance cable according to claim 9 is characterized in that filling out filler between heart yearn or twisting heart yearn and crust and is at least 30 halogen-free flame-retardance composition by oxygen index and forms.