CN101402752A - Halide-free flame retardant resin composition, wire and cable using the composition - Google Patents
Halide-free flame retardant resin composition, wire and cable using the composition Download PDFInfo
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Abstract
The present invention provides a non-halogen flame-retardant resin composition which does not produce noxious gas during burning and has excellent mechanical strength, high flame retardancy and high heat-resistant quality. The resin composition is formed by adding150 to 300 weight parts of the metal hydroxide, 0.5 to 10 weight parts of hindered phenol series of antioxidant, and 0.2 to 5 weight parts of sulphur series antioxidant according to 100 weight parts of the polyolefin resin; performing surface treating to the metal hydroxides, namely using 0.05-1.50 weight parts of at least one aliphatic acid series treating agent composed of aliphatic acids, aliphatic acid metal salts, or aliphatic acid aminium salts and 0.05-1.50 weight parts of silane coupling agent according to 100 weight parts of the metal hydroxides to perform surface treating, so that at least an aliphatic acid surface processing agent and a silane coupling agent simultaneously exist on the surface of htemetal hydroxides.
Description
Technical field
The halogen free flame retardant resin composition that inside distribution that the present invention relates to electronic cooker for example etc. is employed, the heat ageing test of UL125 ℃ is qualified and use the electric wire and cable of this resin combination with high heat resistance.
Background technology
As the flame retardant resin composition of halogen contained compound not, use metal hydroxidess such as in polyolefin-based resins, adding magnesium hydroxide, aluminium hydroxide and the composition that constitutes always.These compositions the time do not produce toxic gases such as hydrogenchloride Huo dioxin in burning, the generation or the secondary disaster of the poisonous gas in the time of therefore can preventing fire are even and carry out burning disposal and also can not have problems when discarded.
But, the flame retardant effect that adds the metal hydroxides generation is less, often can not get desired flame retardant resistance, therefore, people begin to increase the addition of metal hydroxides, perhaps use the polymkeric substance of the polar group that the high EVA (ethylene-vinyl acetate copolymer) of flame retardant resistance etc. has in polyolefin-based resins.
In addition, the prior art document as relevant with the application's invention has following document.
[patent documentation 1] TOHKEMY 2002-42574 communique
[patent documentation 2] TOHKEMY 2005-171036 communique
Summary of the invention
But, follow the increase of addition of the metal hydroxides of prior art, mechanical property such as unit elongation, tensile strength reduces significantly, and, with respect to 100 weight part polyolefin-based resins, if add the above metal hydroxides of 150 weight parts, thermotolerance (the particularly elongation property behind the heat aging) will reduce, and has suchlike problem.
In addition, when use EVA etc. has the polymkeric substance of polar group,, need to use the high polymkeric substance of polarity base unit weight in order to obtain enough flame retardant resistances.But, in general, to compare with the polyethylene that does not have polar group, the thermotolerance of EVA etc. is low, can not reach qualified level in the heat ageing test of UL125 ℃ (reference standard that is used for electric wire, cable and flexible flexible cord).
Therefore, the objective of the invention is to, address the above problem, be provided at qualified in UL125 ℃ the heat ageing test, have the halogen free flame retardant resin composition of high thermotolerance and flame retardant resistance and mechanical propertys such as unit elongation, tensile strength concurrently and use the electric wire and cable of this resin combination.
The present invention finishes to achieve these goals.
The invention of claim 1 is a halogen free flame retardant resin composition, this resin combination is the halogen free flame retardant resin composition that has added metal hydroxides in polyolefin-based resins, it is characterized in that, this resin combination is that the said polyolefins for 100 weight parts is that resin adds the above-mentioned metal hydroxidess of 150～300 weight parts, 0.5～10 weight part hindered phenols are antioxidant, 0.2～5 weight part sulphur are that antioxidant forms, above-mentioned metal hydroxides, use with respect to this metal hydroxides be 0.05～1.50 weight % by lipid acid, at least a in the fatty acid series treatment agent that fatty acid metal salt or fatty acid ammonium salt constitute, and be that the silane coupling agent of 0.05～1.50 weight % has carried out surface treatment with respect to above-mentioned metal hydroxides, on the surface of above-mentioned metal hydroxides, there are at least a above-mentioned fatty acid series treatment agent and above-mentioned silane coupling agent simultaneously.
The invention of claim 2 is the described halogen free flame retardant resin compositions of claim 1, wherein, has also added the metal passivator of 0.1～2.0 weight part.
The invention of claim 3 is claim 1 or 2 described halogen free flame retardant resin compositions, wherein, said polyolefins is that resin is a kind of ethylene-vinyl acetate copolymer, the mixture of the ethylene-vinyl acetate copolymer more than 2 kinds, the perhaps mixture of ethylene-vinyl acetate copolymer more than a kind or 2 kinds and other the polyolefin-based resins more than a kind, and, said polyolefins is that the vinyl acetate containing ratio of resin is more than the 20 weight %, said polyolefins with respect to 100 weight parts is a resin, 1 of 5～50 weight parts have also been added, 3, the 5-pyrrolotriazine derivatives, the gel fraction of being represented by formula (1) is 60～95%.
Gel fraction (%)=((W
1-W
O* a)/(W
O* b)) * 100 (1)
W
O: the initial mass of halogen free flame retardant resin composition (g)
W
1: the quality (g) of the halogen free flame retardant resin composition after in dimethylbenzene, flooding 24 hours under 110 ℃
A: the components in proportions that is insoluble to dimethylbenzene beyond the polyolefin-based resins in the halogen free flame retardant resin composition
B: the ratio of the polyolefin-based resins in the halogen free flame retardant resin composition
The invention of claim 4 is each described halogen free flame retardant resin compositions in the claim 1～3, wherein, has also added the crosslinking coagent of 0.1～5 weight part.
The invention of claim 5 is electric wires that the isolator of conductor uses each described halogen free flame retardant resin composition in the claim 1～4.
The invention of claim 6 is the isolator of conductor and/or the cable that crust uses each described halogen free flame retardant resin composition in the claim 1～4.
The invention effect
According to the present invention, do not produce toxic gas in the time of can obtaining burning, and halogen free flame retardant resin composition with excellent physical strength, high flame retardant and high heat resistance, this halogen free flame retardant resin composition is used for isolator or crust, do not produce toxic gas in the time of can obtaining using or when discarded, have electric wire, the cable of excellent physical strength, high flame retardant and high heat resistance.
Description of drawings
Fig. 1 is the cross-sectional view of an example of the halogen free flame retardant electric wire of expression present embodiment.
Fig. 2 is the cross-sectional view of an example of the halogen free flame retardant cable of expression present embodiment.
Nomenclature
1 electric wire
2 conductors
3 isolators
Embodiment
Below, preferred implementation of the present invention is described.
The halogen free flame retardant resin composition of preferred implementation of the present invention, it is the metal hydroxides that adds 150～300 weight parts for the polyolefin-based resins of 100 weight parts, 0.5 the hindered phenol of～10 weight parts is an antioxidant, 0.2 being antioxidant, the sulphur of～5 weight parts forms, described metal hydroxides, use with respect to metal hydroxides be 0.05～1.50 weight % by lipid acid, at least a above in the fatty acid series treatment agent that fatty acid metal salt or fatty acid ammonium salt constitute and be that the silane coupling agent of 0.05～1.50 weight % has carried out surface treatment with respect to metal hydroxides is at the above-mentioned fatty acid series treatment agent and the silane coupling agent that exist simultaneously on the surface of above-mentioned metal hydroxides more than at least a.
As polyolefin-based resins, can use new LDPE (film grade) (LDPE), straight-chain low density polyethylene (LLDPE), straight chain ultra-low density polyethylene (VLDPE), high density polyethylene(HDPE) (HDPE), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-styrene copolymer, the ethylene-methyl methacrylate glycidyl ester copolymer, ethene-1-Butylene copolymer, ethene-butylene-hexene terpolymer, ethylene-propylene-diene terpolymer (EPDM), ethylene-octene copolymer (EOR), the ethylene copolymer polypropylene, ethylene-propylene copolymer (EPR), poly--4-methyl-amylene-1, toxilic acid grafting new LDPE (film grade), hydrogenated styrene-butadienecopolymer (H-SBR), the toxilic acid grafted linear low density polyethylene, the multipolymer of the alpha-olefin of ethene and carbonatoms 4～20, toxilic acid grafted ethene-methyl acrylate copolymer, toxilic acid grafted ethene-vinyl acetate copolymer, ethene-copolymer-maleic anhydride, ethylene-ethyl acrylate-maleic anhydride copolymer, be ethylene-propylene-butene-1 terpolymers of principal constituent etc. with the butene-1, preferably use EVA.These resins can be used alone, or two or more kinds in combination.
In the present embodiment, as polyolefin-based resins, used more than one the mixture of polyolefin-based resins of the mixture of a kind of EVA, the EVA more than 2 kinds or the EVA more than a kind or 2 kinds and other.In addition, the vinyl acetate of polyolefin-based resins (VA) containing ratio is advisable more than 20 weight %.This is because the VA containing ratio can not obtain excellent flame-retardant performance during less than 20 weight %.
As metal hydroxides, can use magnesium hydroxide, aluminium hydroxide, calcium hydroxide etc.These oxyhydroxide may be used singly or two or more kinds thereof.
In the present embodiment, the addition with metal hydroxides is defined as 150～300 weight parts.This be because, the addition of metal hydroxides can not obtain enough flame retardant resistances during less than 150 weight parts, when surpassing 300 weight parts, elongation property reduces significantly.
In addition, when carrying out the surface treatment of metal hydroxides in the present embodiment, and with fatty acid series treatment agent and silane coupling agent.
As the fatty acid series treatment agent, use lipid acid, fatty acid metal salt, fatty acid ammonium salt.
As lipid acid, can use oleic acid, stearic acid, palmitinic acid, lauric acid, docosoic, linolic acid etc., preferably use oleic acid.
As fatty acid metal salt, can use calcium, zinc, magnesium, aluminium, barium, lithium, sodium, potassium etc., preferably use sodium.
These lipid acid, fatty acid metal salt and fatty acid ammonium salt may be used alone, can also be two or more kinds in combination.
In the present embodiment, use more than at least a in these fatty acid series treatment agents, with respect to metal hydroxides, its addition is 0.05～1.50 weight %, more preferably 0.20～1.00 weight %.This is because the addition of fatty acid series treatment agent can not obtain enough thermotolerances less than 0.05 weight % or when surpassing 1.50 weight %.
On the other hand, as silane coupling agent, so long as usually as getting final product that silane coupling agent uses, have no particular limits, for example, can use vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane, TSL 8330, aminopropyltriethoxywerene werene etc.
In the present embodiment, with respect to metal hydroxides, the addition of this silane coupling agent is 0.05～1.50 weight %, more preferably 0.20～1.30 weight %.This is because the addition of silane coupling agent can not obtain enough thermotolerances during less than 0.05 weight %, when surpassing 1.50 weight %, can not obtain enough elongation properties.
When the surface treatment of metal hydroxides, adopt a small amount of either party who adds in fatty acid series treatment agent and the silane coupling agent, and then interpolation the opposing party, perhaps add methods such as fatty acid series treatment agent and silane coupling agent simultaneously, make to have fatty acid series treatment agent and silane coupling agent simultaneously on the surface of metal hydroxides.In addition, the occasion of Tian Jiaing needs to stir 2 kinds of treatment agents in advance fully at the same time, makes it homogenizing.
This be because, for example, be enough to cover the occasion on metal hydroxides surface adding surface treatment agent and addition successively, the surface treatment agent of Tian Jiaing has covered the surface treatment agent of previous interpolation at last, as a result, become characteristic same with the processing of single surface treatment agent the time.
In the present embodiment,, use fatty acid series treatment agent and silane coupling agent, but in the occasion of the characteristic of only bringing into play the fatty acid series treatment agent, elongation property becomes well, but can not get enough thermotolerances as the surface treatment agent of metal hydroxides.On the other hand, in the occasion of the characteristic of only bringing into play silane coupling agent, thermotolerance becomes well, but can not get enough elongation properties.
Therefore, when the surface treatment of metal hydroxides, make the surface of metal hydroxides have fatty acid series treatment agent and silane coupling agent simultaneously, can bring into play the characteristic of fatty acid series treatment agent and silane coupling agent, unit elongation does not reduce, and obtains more excellent thermotolerance.
In addition, in the present embodiment, as antioxidant, using hindered phenol simultaneously is that antioxidant and sulphur are antioxidant.
As hindered phenol is antioxidant, so long as have 3 in the molecular skeleton, 5-di-t-butyl-4-hydroxyl-benzyl person gets final product, has no particular limits, preferred use 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-benzyl)-guanamine, 4,6-(1H, 3H, 5H) triketone.
In the present embodiment, this hindered phenol is that the addition of antioxidant is 0.5～10 weight part.This be because, hindered phenol is the addition of antioxidant during less than 0.5 weight part, can not obtain enough thermotolerances, if surpass 10 weight parts, flame retardant resistance will reduce.
On the other hand, be antioxidant as sulphur, get final product so long as have the antioxidant of sulphur atom in the molecular skeleton, have no particular limits, preferably use four [methylene radical-3-(dodecyl sulfo-) propionic ester] methane.
In the present embodiment, this sulphur is that the addition of antioxidant is 0.2～5 weight part, more preferably 0.5 weight part.This is because sulphur is the addition of antioxidant during less than 0.2 weight part, can not obtain enough thermotolerances, if surpass 5 weight parts, the bad order that causes because of frosting will take place.
In addition, can also add the metal passivator of 0.1～2.0 weight part.
Metal passivator makes the metal ion stabilization by forming inner complex, and the effect that prevents oxidative degradation is arranged, its structure without limits, preferably use 2 ', two [3-[3, the 5-di-tert-butyl-hydroxy phenyl] propionyls of 3-] the propionyl hydrazides.
In addition, the gel fraction of the halogen free flame retardant resin composition of present embodiment can be 60～95%.This be because, gel fraction can not obtain the flame retardant resistance of the qualified level of testing vertical flammability (VW-1) less than 60% o'clock, if surpass 95%, elongation property will reduce significantly.
Gel fraction is the quality W under the initial drying regime of the halogen free flame retardant resin composition of mensuration present embodiment
OAnd this halogen free flame retardant resin composition flooded 24 hours, dried quality W in 110 ℃ dimethylbenzene
1, the value that calculates according to formula (1).In formula (1), a is the polyolefin-based resins components in proportions that is insoluble to dimethylbenzene in addition in the halogen free flame retardant resin composition, and b is the ratio of the polyolefin-based resins in the halogen free flame retardant resin composition.
Gel fraction (%)=((W
1-W
O* a)/(W
O* b)) * 100 (1)
The method that improves gel fraction has no particular limits, for example, and utilize preferably that organo-peroxide causes crosslinked or utilize crosslinked that the electron rays isoradial causes.
In addition, can also further add the 1,3,5-triazines derivative of 5～50 weight parts.This be because, the 1,3,5-triazines derivative add the merit amount less than 5 weight parts the time, can not obtain the flame retardant resistance of VW-1 stand the test level, when surpassing 50 weight parts, physical strength will reduce.
It is believed that the 1,3,5-triazines derivative in decomposing more than 300 ℃, distilling, produces non-flammable gases, thereby helps flame retardant resistance when burning.As the 1,3,5-triazines derivative, can use trimeric cyanamide, cyanuric acid, tricarbimide, melamine cyanurate, sulfuric acid trimeric cyanamide etc., preferably use melamine cyanurate.In addition, these compounds also can carry out surface treatment with nonionogenic tenside or various coupling agent.
In addition, also can add the crosslinking coagent of 0.1～5 weight part again.This is because the addition of crosslinking coagent can not obtain the flame retardant resistance of VW-1 stand the test level during less than 0.1 weight part, when surpassing 5 weight parts, frosting will take place.
As crosslinking coagent, have no particular limits, for example can use trimethylolpropane trimethacrylate (TMPT) or triallyl isocyanurate (TAIC).
In addition, except above-mentioned Synergist S-421 95, can also add additives such as antioxidant, lubricant, inorganic filler, phase solvation, stablizer, carbon black, tinting material as required.
The manufacture method of the halogen free flame retardant resin composition of present embodiment has no particular limits, for example, can be after cooperating above-mentioned various compositions, carry out mixingly with the kneader that pressurizes etc., mixing post-treatment becomes particulate state to get final product.
The following describes the effect of present embodiment.
The halogen free flame retardant resin composition of present embodiment is that to add 150～300 parts by weight of metal hydroxide, 0.5～10 weight part hindered phenol with respect to 100 weight part polyolefin-based resins be that antioxidant, 0.2～5 weight part sulphur are antioxidant and forming.
As antioxidant, using hindered phenol simultaneously is that antioxidant and sulphur are antioxidant, because adding 0.5～10 weight part hindered phenol is that antioxidant, 0.2～5 weight part sulphur are antioxidant, flame retardant resistance can not take place to be reduced or bad order, can further improve thermotolerance.
In addition, the metal hydroxides that uses in the halogen free flame retardant resin composition of present embodiment, use fatty acid series treatment agent at least a above of 0.05～1.50 weight % with respect to above-mentioned metal hydroxides and use the silane coupling agent of 0.05～1.50 weight % to carry out surface treatment, on the surface of this metal hydroxides, have fatty acid series treatment agent and silane coupling agent simultaneously with respect to above-mentioned metal hydroxides.
By fatty acid series treatment agent and the silane coupling agent that uses 0.05～1.50 weight % metal hydroxides is carried out surface treatment, can under the situation that does not reduce physical strength, improve thermotolerance.
In addition, owing on the surface of metal hydroxides, have fatty acid series treatment agent and silane coupling agent simultaneously, can prevent to become characteristic same with separately with any surface treatment agent processing the time, the characteristic of fatty acid series treatment agent and silane coupling agent can be brought into play, therefore excellent thermotolerance can be accessed.
Therefore, adopt the halogen free flame retardant resin composition of present embodiment, the reduction or the bad order of physical strength and flame retardant resistance can not take place, can improve thermotolerance, realize the UL125 ℃ of high heat resistance that heat ageing test is qualified.
In addition, the halogen free flame retardant resin composition of present embodiment further adds the metal passivator of 0.1～2.0 weight part.Like this, make the halogen free flame retardant resin composition stabilization that makes, can prevent oxidative degradation.
Have, the halogen free flame retardant resin composition of present embodiment, the VA containing ratio of its polyolefin-based resins are more than the 20 weight % again, further add 1 of 5～50 weight parts with respect to 100 weight part polyolefin-based resins, 3,5-pyrrolotriazine derivatives, gel fraction are 60～95%.
Be set at 20 weight % by VA containing ratio, can access excellent flame-retardant performance polyolefin-based resins.
In addition, by the 1,3,5-triazines derivative of further interpolation 5～50 weight parts, physical strength does not reduce, and flame retardant resistance is improved.
Have, by gel fraction is set at 60～95%, elongation property does not reduce again, and flame retardant resistance is improved.
In addition, the halogen free flame retardant resin composition of present embodiment further adds the crosslinking coagent of 0.1～5 weight part.Like this, bad order can not take place, flame retardant resistance is improved.
Therefore, adopt the halogen free flame retardant resin composition of present embodiment, physical strength can not take place reduce or bad order, can improve flame retardant resistance, realize the flame retardant resistance of VW-1 stand the test level.
Promptly, adopt the halogen free flame retardant resin composition of present embodiment, can be implemented in qualified high heat resistance in the UL125 ℃ of heat ageing test, and, can realize the flame retardant resistance and the excellent mechanical intensity (elongation property and tensile strength) of VW-1 stand the test level.
In addition, because the halogen free flame retardant resin composition of present embodiment does not use halogen compounds, thereby when burning, do not produce toxic gas such as hydrogenchloride Huo dioxin.
Below, the halogen free flame retardant electric wire of present embodiment is described.
As shown in Figure 1, the halogen free flame retardant electric wire 1 of present embodiment, be the electric wire that the halogen free flame retardant resin composition of present embodiment is used for the isolator 3 of conductor 2, have isolator 3 that periphery at conductor 2 and this conductor 2 forms, that constitute by the halogen free flame retardant resin composition of present embodiment.
The halogen free flame retardant electric wire 1 of present embodiment, for example can make: will be processed into the granulous halogen free flame retardant resin composition and drop in the forcing machine by the following stated, make the fused halogen free flame retardant resin composition cover the periphery of conductor 2, form isolator 3, then with its cooling.And then, can also be to the isolator 3 irradiation electron rayies of resulting halogen free flame retardant electric wire 1, it is crosslinked to carry out electron rays.
In the halogen free flame retardant electric wire 1 of present embodiment, use above-mentioned halogen free flame retardant resin composition as isolator 3, thereby in use or do not produce toxic gas when discarded, can realize the qualified high heat resistance of UL125 ℃ of heat ageing test, the high flame retardant and the excellent physical strength of VW-1 stand the test level.
Below, the halogen free flame retardant cable of present embodiment is described.
As shown in Figure 2, the halogen free flame retardant cable 21 of present embodiment is the isolator 23 of conductor 22 and/or the cable that crust 24 uses the halogen free flame retardant resin composition of present embodiment.
The halogen free flame retardant cable 21 of present embodiment has: on conductor 22, covered 3 of isolator 23 thoroughly do away with edge heart yearns 25, with this 3 crust 24 that thoroughly does away with writing that surpasses all the others band 27 that the stranded together back of media 26 such as edge heart yearn 25 and paper applies and form on its periphery in the periphery of this writing that surpasses all the others band 27.
In the halogen free flame retardant cable 21 of present embodiment, use above-mentioned halogen free flame retardant resin composition as isolator 23 and/or crust 24, thereby obtain effect and the effect identical with the halogen free flame retardant electric wire 1 of Fig. 1.
Embodiment
Use the halogen free flame retardant resin composition of the present invention shown in table 1～2, make the halogen free flame retardant electric wire of embodiment 1～31.
As the example of the surface treatment method of metal hydroxides, illustrate in embodiment 1, implement, with sodium stearate and vinyltrimethoxy silane magnesium hydroxide is carried out the surface-treated method.The surface-treated method, by following (A) and any method (B) carry out.
(A)
Add water in not surface treated magnesium hydroxide, the magnesium hydroxide slurry of preparation 100g/l stirs these slurry at 50 ℃, splashes into the sodium stearate of 0.05 weight % with respect to magnesium hydroxide, stirs 2 hours.Then, splash into vinyltrimethoxy silane.Drip to finish the back and stirred 2 hours, filter subsequently, clean, dry, pulverizing.
(B)
According to weight ratio metering sodium stearate and the vinyltrimethoxy silane of embodiment 1, to wherein adding water, forming solution, stirred 2 hours at 50 ℃, prepare the aqueous solution that both homogeneous exist.Add interpolation water in not surface treated magnesium hydroxide, the magnesium hydroxide slurry of preparation 100g/l stirs this slurry at 50 ℃, and to wherein dripping the aqueous solution that has just prepared, the amount of sodium stearate is 0.05 weight % with respect to magnesium hydroxide, stirs 2 hours.After this, filter, clean, dry, pulverize.
In addition, the surface treatment amount described in table 1～2 is the adsorptive capacity that calculates by x-ray fluorescence analysis etc.
Make halogen free flame retardant resin composition and halogen free flame retardant electric wire 1 in the following stated: cooperate various compositions in the cooperation ratio shown in table 1～2, mixing with the pressurization kneader under 40 ℃ of starting temperatures, 190 ℃ of conditions of final temperature, then mixing thing is made pellet, with the isolator 3 of this pellet, extrude for 200 ℃ by thickness 0.41mm, design temperature as halogen free flame retardant electric wire 1 shown in Figure 1.In addition, the halogen free flame retardant electric wire 1 irradiation electron rays to making.Irradiation dose is 10～200kGy.
The evaluation of halogen free flame retardant electric wire 1 is carried out according to the method for the following stated.
(1) tension test
According to JIS C 3005, the halogen free flame retardant electric wire of making 1 is carried out tension test.Unit elongation is evaluated as * (defective) less than 1 50%, and 1 50～300% are evaluated as zero (qualified), and 300% above person is evaluated as ◎ (having nargin, qualified).Tensile strength is evaluated as * (defective) less than 10MPa person, and 10～13MPa person is evaluated as zero (qualified), and the above person of 1 3MPa is evaluated as ◎ (having nargin, qualified).
(2) thermal test
Carry out 125 ℃ of UL (224,125 ℃ of rated value of UL) heat ageing test.Measure the tensile strength and the unit elongation of the isolator after 158 ℃ * 7 days, the tensile strength residual rate is that 70% above person is evaluated as zero, and the unit elongation residual rate is 65% to be evaluated as zero, other is evaluated as *.
(3) flame retardant test
As flame retardant test, carry out the testing vertical flammability (VW-1) of UL 94 combustion tests and the electric wire shape of lamella shape.
UL 94 test is, according to UL 94 combustion test standards the thin slice that is configured as 125mm * 13mm * 3mm carried out, and is equivalent to V-O person and is evaluated as zero, other is evaluated as *.
The VW-1 test is, according to UL subjcct 758 standards the halogen free flame retardant electric wire of making 1 is tested, be evaluated as ◎ (have nargin, qualified) less than 30 seconds persons combustion time, be evaluated as zero (qualified) less than 1 minute person, the person is evaluated as * (defective) more than 1 minute.
(4) outward appearance test
The surface and the section of the halogen free flame retardant electric wire made from 50 times observation by light microscope 1, the surface does not slightly make to observe on person, the surface has foaming person to be evaluated as * (defective) on frosting person and the section, no abnormal person is evaluated as zero (qualified) on surface and the section.
As shown in table 1, in embodiment 1～17, flame retardant resistance is the qualified level of UL 94V-O, and all the other all show good characteristic.
In embodiment 1 and 2, changed the treatment capacity of the surface treatment agent sodium stearate that is magnesium hydroxide, but 0.05～1.5 weight % in regulation is good, in addition, shown in embodiment 3, as long as within the limits prescribed, even fatty acid series treatment agent and usefulness more than 2 kinds also demonstrate good characteristic.
In embodiment 4～6, changed kind, the addition of the surface treatment agent silane coupling agent of magnesium hydroxide, but so long as within the limits prescribed, just demonstrated good characteristic.
In the occasion of the addition of magnesium hydroxide being changed into 150 weight parts (embodiment 7), 300 weight parts (embodiment 8), when increasing the addition of magnesium hydroxide, flame retardant resistance further improves.
Hindered phenol is that the addition of antioxidant is the occasion of 0.5 weight part (embodiment 9), 10 weight parts (embodiment 10), and by increasing addition, thermotolerance improves.Equally, the addition of sulphur antioxidant is the occasion of 0.2 weight part (embodiment 11), 5 weight parts (embodiment 12), and when addition increased, thermotolerance further improved.
The addition of metal passivator is the occasion of 0.1 weight part (embodiment 1 3), 2.0 weight parts (embodiment 14), and when addition increased, thermotolerance further improved.
Even stock polymer be the monomeric embodiment of EVA, 2 kinds of EVA blended embodiment 5 and with other polyolefin-based resins blended embodiment 16,17 in, characteristic also is good.
As shown in table 2, in embodiment 18～31, flame retardant resistance further improves, and is the qualified level of VW-1, and all the other all show good characteristic.
VA amount in polyolefin-based resins is the occasion of 21 weight % (embodiment 1 8), 42 weight % (embodiment 19), and the VA amount is high more, and flame retardant resistance is high more.In addition, with other polyolefin-based resins blended embodiment 20 and embodiment 21 in, so long as more than 20 weight % of regulation, flame retardant resistance is exactly the qualified level of VW-1.
Addition at the 1,3,5-triazines derivative is the occasion of 5 weight parts (embodiment 22), 50 weight parts (embodiment 23), the embodiment 23 that addition is many, and flame retardant resistance further improves, the preferential interpolation 1,3,5-triazines derivative of selecting.
At gel fraction is the occasion of 60% (embodiment 24), 95% (embodiment 25), and when improving gel fraction, flame retardant resistance further improves.
In the occasion of the addition of magnesium hydroxide being changed into 150 weight parts (embodiment 26), 300 weight parts (embodiment 27), when increasing the addition of magnesium hydroxide, flame retardant resistance further improves.
Addition at crosslinking coagent is 0.1 weight part (embodiment 28) in the specialized range, the occasion of 5.0 weight parts (embodiment 29), and flame retardant resistance further improves among the addition embodiment 29 how, the preferential interpolation crosslinking coagent of selecting.
Addition at metal passivator is the occasion of 0.1 weight part (embodiment 30), 2.0 weight parts (embodiment 31), and when increasing addition, thermotolerance further improves.
Relative therewith, use the resin shown in the table 3 to make the electric wire of comparative example 1～13, similarly estimate with embodiment.
As shown in table 3, the addition that the addition of magnesium hydroxide is antioxidant than the comparative example 1 that lacks of regulation and hindered phenol is than the comparative example of stipulating to Duo 8, and flame retardant resistance is inadequate.
The comparative example 6,1 that the addition of the comparative example 2 that the addition of magnesium hydroxide is Duoed than regulation, the silane coupling agent of magnesium hydroxide is Duoed than regulation, 3, the comparative example 13 that the comparative example 11 that the addition of 5-pyrrolotriazine derivatives is Duoed than regulation, gel fraction are Duoed than regulation than the addition of stipulating high comparative example 12 and crosslinking coagent, elongation property is inadequate.
The addition that the amount of coating of the comparative example 3 that the amount of coating of the fatty acid series treatment agent of magnesium hydroxide lacks than regulation, comparative example 4, the silane coupling agent of Duo than regulation is antioxidant than the comparative example of stipulating to lack 7 and sulphur than the comparative example of stipulating to lack 5, addition that hindered phenol is antioxidant is than the comparative example of stipulating to lack 9, and thermotolerance is inadequate.
Frosting than the comparative example of stipulating to Duo 13, has all taken place than the addition of comparative example of stipulating to Duo 10 and crosslinking coagent in the hindered phenol comparative example 8 that to be antioxidant Duo than regulation, addition that sulphur is antioxidant.
Therefore can confirm, according to the present invention, can obtain having the qualified high heat resistance of UL125 ℃ of heat ageing test, the flame retardant resistance of VW-1 stand the test level, the good halogen free flame retardant resin composition of excellent mechanical intensity (elongation property and tensile strength).
Claims (6)
1. halogen free flame retardant resin composition, this resin combination is the halogen free flame retardant resin composition that has added metal hydroxides in polyolefin-based resins, it is characterized in that, this resin combination is that the said polyolefins for 100 weight parts is that resin adds the above-mentioned metal hydroxidess of 150～300 weight parts, 0.5～10 weight part hindered phenols are antioxidant, 0.2～5 weight part sulphur are that antioxidant forms, above-mentioned metal hydroxides, use with respect to this metal hydroxides be 0.05～1.50 weight % by lipid acid, at least a in the fatty acid series treatment agent that fatty acid metal salt or fatty acid ammonium salt constitute, and be that the silane coupling agent of 0.05～1.50 weight % has carried out surface treatment with respect to above-mentioned metal hydroxides, on the surface of above-mentioned metal hydroxides, there are at least a above-mentioned fatty acid series treatment agent and above-mentioned silane coupling agent simultaneously.
2. halogen free flame retardant resin composition according to claim 1 wherein, has also added the metal passivator of 0.1～2.0 weight part.
3. halogen free flame retardant resin composition according to claim 1 and 2, wherein, described polyolefin-based resins is a kind of ethylene-vinyl acetate copolymer, the mixture of the ethylene-vinyl acetate copolymer more than 2 kinds, the perhaps mixture of ethylene-vinyl acetate copolymer more than a kind or 2 kinds and other the polyolefin-based resins more than a kind, and, the vinyl acetate containing ratio of described polyolefin-based resins is more than the 20 weight %, described polyolefin-based resins with respect to 100 weight parts, 1 of 5～50 weight parts have also been added, 3, the 5-pyrrolotriazine derivatives, gel fraction by formula (1) expression is 60～95%
Gel fraction (%)=((W
1-W
O* a)/(W
O* b)) * 100 (1)
W
O: the initial mass of halogen free flame retardant resin composition (g);
W
1: in the quality (g) of the halogen free flame retardant resin composition of dipping after 24 hours under 110 ℃, in dimethylbenzene;
A: the components in proportions that is insoluble to dimethylbenzene beyond the polyolefin-based resins in the halogen free flame retardant resin composition;
B: the ratio of the polyolefin-based resins in the halogen free flame retardant resin composition.
4. each described halogen free flame retardant resin composition in the claim 1～3 wherein, has also added the crosslinking coagent of 0.1～5 weight part.
5. electric wire is characterized in that, the isolator of conductor uses each described halogen free flame retardant resin composition in the claim 1～4.
6. cable is characterized in that, the isolator of conductor and/or crust use each described halogen free flame retardant resin composition in the claim 1～4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007259709A JP2009084524A (en) | 2007-10-03 | 2007-10-03 | Halogen-free flame-retardant resin composition and electric wire/cable using the same |
| JP2007259709 | 2007-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101402752A true CN101402752A (en) | 2009-04-08 |
Family
ID=40536926
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101661082A Pending CN101402752A (en) | 2007-10-03 | 2008-10-06 | Halide-free flame retardant resin composition, wire and cable using the composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2009084524A (en) |
| CN (1) | CN101402752A (en) |
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| JPH04334810A (en) * | 1991-05-10 | 1992-11-20 | Hitachi Cable Ltd | Flame retardant electric insulating composite |
| JP3966632B2 (en) * | 1998-12-24 | 2007-08-29 | 古河電気工業株式会社 | Wire covering resin composition and insulated wire |
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| JP2005171036A (en) * | 2003-12-10 | 2005-06-30 | Tmg Kk | Metal hydroxide and flame retardant resin composition |
| JP4735340B2 (en) * | 2006-03-03 | 2011-07-27 | 日立電線株式会社 | Non-halogen flame retardant resin composition and electric wire / cable using the same |
| JP2008280444A (en) * | 2007-05-11 | 2008-11-20 | Hitachi Cable Ltd | Halogen-free flame-retardant resin composition and electric wire or cable using the same |
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2007
- 2007-10-03 JP JP2007259709A patent/JP2009084524A/en active Pending
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2008
- 2008-10-06 CN CNA2008101661082A patent/CN101402752A/en active Pending
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| JP2009084524A (en) | 2009-04-23 |
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Application publication date: 20090408 |