CN1911996A - Non-halogen flame-retardant thermoplastic elastomer composition, its manufacturing method, electrical wire and electrical cable - Google Patents
Non-halogen flame-retardant thermoplastic elastomer composition, its manufacturing method, electrical wire and electrical cable Download PDFInfo
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- CN1911996A CN1911996A CN 200610115439 CN200610115439A CN1911996A CN 1911996 A CN1911996 A CN 1911996A CN 200610115439 CN200610115439 CN 200610115439 CN 200610115439 A CN200610115439 A CN 200610115439A CN 1911996 A CN1911996 A CN 1911996A
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Abstract
The invention provides a non-halogen flame retardant thermoplastic elastomer composition being free from the trouble of unpleasant odor or coloring, may compriese any type of a polyolefin resin, and has the softness being simular to that of a halogen-containing material, and also to provide its production process and an electric wire/cable using the composition. The non-halogen flame retardant thermoplastic elastomer composition of the invention contains (A) 40-80 pts.wt. of a rubber cross-linked with a silane, (B) 60-20 parts by weight of a crystalline polyolefin based resin and (C) 40-250 parts by weight of a metal hydroxide based on 100 parts by weight of the sum of (A) and (B).
Description
Technical field
The present invention relates to pliability and excellent in flame retardance, the non-halogen flame-retardant thermoplastic elastomer composition that has higher physical strength, thermotolerance, oil-proofness, recirculation simultaneously relates in particular to by rubber is carried out electric wire and the cable that crosslinked with silicane obtains non-halogen flame-retardant thermoplastic elastomer composition and manufacture method thereof and uses said composition in the process of mixing.
Background technology
Activity at environmental protection grows to even greater heights in worldwide, with regard to the electric wire covering material, and material low in the pollution of the environment when not producing toxic gas, processing Litter when popularizing burning rapidly, as can to realize material recirculation.
As this material, adopting at crystalline polyolefin usually is the composition that has mixed in the matrix polymers such as resin or thermoplastic elastomer with the non-halogen flame retardant headed by the metal hydroxides.Particularly for the purposes that needs flexible materials, most cases is to use the composition of Young's modulus at rubber and resin intermediary thermoplastic elastomer and fire retardant.
Various thermoplastic elastomers have been developed up to now.The known dynamic crosslinking technology that for example adopts the crosslinked special component while mixing has been disperseed the composition of cross-linked rubber composition etc. in the polyolefin-based resins matrix as the composition that flows.For this dynamic crosslinking technology, the selection of a rubber crosslinker is an outbalance.The ideal linking agent, cross-linked rubber composition optionally, and have the speed of response of in the process of mixing, finishing the such degree of crosslinking reaction.
Thus,, in the process of mixing, also can generate the cross-linked rubber particle, be distributed in the thermoplastic resin even rubber is the volume composition.As such linking agent, normally usedly can enumerate for example sulphur or organo-peroxide.
Patent documentation 1: the spy opens the 2000-336225 communique
Patent documentation 2: the spy opens the 2000-195336 communique
Summary of the invention
But, adopt sulphur to carry out when crosslinked, exist because of generate problem that sulfuration is the peculiar smell that causes of gas and because of painted cause be difficult to the problem of the form and aspect of molding thing freely.In addition, adopt organo-peroxide to carry out when crosslinked, can carry out crosslinkedly simultaneously to polyolefin-based resins,, have the polyacrylic problem of the classification that in fact can only select to belong to hard so need to select be difficult to take place crosslinked resin as the composition that flows.Its result wants to make the pliability of composition to approach halogen based materials such as polyvinyl chloride, be have circumscribed.
Therefore, purpose of the present invention is exactly in order to solve above-mentioned problem, a kind of problem that does not have peculiar smell and tint permanence is provided, and can freely select polyolefin-based resins, have and the non-halogen flame-retardant thermoplastic elastomer composition of halogen based material equal extent pliability and the electric wire and the cable of manufacture method and use said composition thereof.
In order to achieve the above object, first invention of the present invention is a non-halogen flame-retardant thermoplastic elastomer composition, it is characterized by, containing (A) rubber 40～80 weight parts, (B) crystalline polyolefin and be resin 60～20 weight parts, (C) is the metal hydroxides of 40～250 weight parts with respect to (A) with (B) total 100 weight parts, and this rubber has carried out crosslinked with silicane.
Of the present invention second the invention be first the invention described non-halogen flame-retardant thermoplastic elastomer composition, it is characterized by, above-mentioned (A) rubber be mutually be dispersed in (B) crystalline polyolefin be resin mutually in.
The 3rd invention of the present invention is first invention or the described non-halogen flame-retardant thermoplastic elastomer composition of second invention, it is characterized by, and above-mentioned (A) rubber is ethylene, propylene-diene copolymers.
The 4th invention of the present invention is each the described non-halogen flame-retardant thermoplastic elastomer composition during first invention is invented to the 3rd, it is characterized by, above-mentioned (B) crystalline polyolefin is that resin is to be selected from least a in polypropylene, high density polyethylene(HDPE), straight chain shape new LDPE (film grade), ultra-low density polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, the ethene-1-octene copolymer.
The 5th invention of the present invention is each the described non-halogen flame-retardant thermoplastic elastomer composition during first invention is invented to the 4th, it is characterized by, and above-mentioned (C) metal hydroxides is a magnesium hydroxide, and has carried out surface treatment by silane series coupling agent.
The 6th invention of the present invention is each the described non-halogen flame-retardant thermoplastic elastomer composition during first invention is invented to the 5th, it is characterized by, it is resin that above-mentioned composition contains rubber or crystalline polyolefin that the copolymerization of unsaturated carboxylic acid or derivatives thereof is formed.
The 7th invention of the present invention is the method for each the described non-halogen flame-retardant thermoplastic elastomer composition during manufacturing first invention is invented to the 6th, it is characterized by, the above-mentioned rubber that carries out crosslinked with silicane forms by rubber that silane compound graft copolymerization forms and metal hydroxides are mixed.
The 8th invention of the present invention is according to the manufacture method of the described non-halogen flame-retardant thermoplastic elastomer composition of the 7th invention, it is characterized by, and above-mentioned composition contains silanol condensation catalyst, by contacting with moisture, makes rubber cross.
The 9th invention of the present invention is electric wire and cable, it is characterized by first invention to each described non-halogen flame-retardant thermoplastic elastomer composition in the 6th invention is used for isolator or sheath body.
According to the present invention, can provide the non-halogen flame-retardant thermoplastic elastomer composition of pliability and excellent in flame retardance.Said composition also has higher physical strength, thermotolerance, oil-proofness, recirculation simultaneously, the suitable covering material that is used as line cord or cabtyre cable isoelectric line and cable.
Description of drawings
Fig. 1 is the detailed sectional view of the electric wire that is suitable for of the present invention.
Fig. 2 is the detailed sectional view of the cable that is suitable for of the present invention.
Fig. 3 is the detailed sectional view of the cable that is suitable for of the present invention.
Among the figure, the 1st, copper conductor, the 2nd, isolator, 3 and 7 is sheath bodies, the 10th, electric wire, 20 and 30 is cables.
Embodiment
Below, be described with reference to the accompanying drawings the embodiment that the present invention suits.
At first, in conjunction with Fig. 1～Fig. 3 electric wire and the cable of using non-halogen flame-retardant thermoplastic elastomer composition of the present invention is described.
Fig. 1 has been illustrated in coating on the copper conductor 1 electric wire 10 of the isolator 2 that constitutes by non-halogen flame-retardant thermoplastic elastomer composition.
Fig. 2 represents electric wire shown in three chromosomes 1 10 is twisted with the fingers together, the cable 20 of the sheath body 3 that is made of non-halogen flame-retardant thermoplastic elastomer composition in the periphery coating.
Fig. 3 represents several (being four in the drawings) electric wire shown in Figure 1 10 is twisted with the fingers together, is wrapped with volume moulding band 5 through medium 4, forms core body 6, the cable 30 of the sheath body 7 that is made of non-halogen flame-retardant thermoplastic elastomer composition in the periphery coating of this core body 6.
Fig. 1～isolator 2, the sheath body the 3, the 7th that constitutes by non-halogen flame-retardant thermoplastic elastomer composition shown in Figure 3, by the extrusion moulding coating.
In the present invention, in order to achieve the above object, studied cross-linking method, found that using crosslinked with silicane is effective means.
In the past because crosslinked with silicane and use sulphur or the situation of organo-peroxide to compare crosslinking reaction slow, so need carry out crosslinked operation in the presence of silanol condensation catalyst, contacting after the moulding with moisture.Thereby, can't obtain disperseing the thermoplastic compounds of crosslinked with silicane rubber phase, crosslinked with silicane is difficult to be applicable to dynamic crosslinking.
With respect to this, discovery metal hydroxidess such as the inventor can promote to make the crosslinking reaction of the rubber that silane compound graft copolymerization forms significantly.
Its result, obtained a kind of non-halogen flame-retardant thermoplastic elastomer composition, it contains (A) rubber 40～80 weight parts, (B) crystalline polyolefin is resin 60～20 weight parts and (C) is the metal hydroxides of 40～250 weight parts with respect to (A) with (B) total 100 weight parts, wherein, described rubber has carried out crosslinked with silicane.
Find said composition not only pliability and excellent in flame retardance, and also have higher physical strength, thermotolerance, oil-proofness, recirculation simultaneously, so that finished the present invention.
(A) rubber of stipulating among the present invention can be divided into rubber that contains the diene composition in the molecule and the rubber that does not contain the diene composition substantially.
As the rubber that contains the diene composition in molecule, representational have vinylbenzene-diene copolymers such as natural rubber, synthetic polyisoprene, divinyl rubber, isoprene-isobutylene rubber, acrylonitrile butadiene rubber, styrene butadiene ribber, styrene isoprene rubber; Vinylbenzene-diene-styrenerubbers such as styrene-butadiene-styrene rubber, styrene-isoprene-phenylethene rubber.In addition, also comprise and extremely can carry out the sulfurized degree, and stay the rubber of a small amount of diene composition these rubber hydrogenation.And then, the acrylic rubber of diene composition that also comprised ethylene-propylene-diene copolymer, ethene-1-butylene-diene copolymers, ethene-1-octene-diene copolymers and copolymerization.These are representational examples, can use in molecular structure all rubber that contain the diene composition at main chain and side chain.
As the rubber that in molecule, does not contain the diene composition, can enumerate ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-octene copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer.
In addition, also have for being the styrene diene copolymer of representative with styrene butadiene ribber and styrene isoprene rubber or being the vinylbenzene-diene-styrene copolymer of representative, almost completely hydrogenation and the vinyl benzene rubber that obtains with styrene-butadiene-styrene rubber and styrene-isoprene-phenylethene rubber.
Wherein, consider optimal ethylene-propylene diene copolymerized thing from aspects such as intensity, thermotolerance, processibilities.As the diene composition of ethylene-propylene-diene copolymer, can enumerate 5-ethidine-2-norbornylene, 5-vinyl-2-norbornylene, Dicyclopentadiene (DCPD), 1,4-hexadiene etc.In addition, be not particularly limited, can use material arbitrarily for diene content, ethylene content, mooney viscosity etc.
In addition, above-mentioned (A) rubber, because crosslinked with silicane, so copolymerization has silane compound.
The silane compound of defined contains simultaneously in molecule and can form crosslinked alkoxyl group with the functional group of rubber reaction with by silanol condensation in the present invention.
Specifically, can enumerate vinyl silane compounds such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane; Gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, β-(amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, N-phenyl-amino silane compounds such as gamma-amino propyl trimethoxy silicane; β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy silane compounds such as glycidoxy propyl group methyldiethoxysilane; Silicon Acrylote hydride compounds such as γ-methacryloxypropyl trimethoxy silane; Polysulfide silanes compounds such as two (3-(triethoxysilyl) propyl group) disulphide, two (3-(triethoxysilyl) propyl group) tetrasulfide; Hydrosulphonyl silane compounds such as 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane.
During the graft copolymerization silane compound, can adopt known usual way, for example the quantitative silane compound of hybrid regulatory, free free-radical generating agent in base rubber are carried out the method that fusion is mixed.As free free-radical generating agent, mainly use organo-peroxides such as diisopropylbenzyl superoxide.
As the optimum amount of the organo-peroxide of free free-radical generating agent, be 0.001～3.0 weight part with respect to rubber 100 weight parts.If be less than 0.001 weight part, then silane compound graft copolymerization fully can't obtain sufficient cross-linking effect.If surpass 3.0 weight parts, rubber burnt.
In addition, have the functional group of containing sulphur when being the silane compound of sulfenyl or sulfydryl, can adopt following steps for graft copolymerization in the rubber that in molecule, contains the diene composition.
The silane compound that will have the functional group of containing sulphur is mixed in the rubber that contains the diene composition in molecule, and by mixing 80～200 ℃ temperature, graft copolymerization is to rubber.At this moment, for the purpose of the mechanical characteristics of speed of response of regulating graft copolymerization or composition, also can add vulcanization accelerator additives such as vulcanization accelerators such as guanidine, thiuram, dithiocarbamic acid, thiazole, sulphenamide, zinc oxide, stearic acid etc.
Supply method as silane compound, can adopt the method for when mixing, directly adding rubber to, perhaps in advance behind absorption silane compound in the mineral fillers such as carbon black or metal hydroxides, this carbon black or metal hydroxides are added to when mixing in the rubber, simultaneously silane compound is supplied in the method for rubber etc.
The addition of silane compound is not particularly limited, but in order to obtain good rerum natura, is preferably 0.5～5.0 weight part with respect to rubber 100 weight parts.If be less than 0.5 weight part, then can't obtain sufficient cross-linking effect, the intensity of composition and thermotolerance can variation.If surpass 5.0 weight parts, then processibility significantly reduces.And, use when having the silane compound of the functional group of containing sulphur, if surpass 5.0 weight parts, then can't ignore stink and coloring problem.
As (B) crystalline polyolefin is resin, can use known substances, especially preferably contain and be selected from least a in polypropylene, high density polyethylene(HDPE), straight chain shape new LDPE (film grade), ultra-low density polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, the ethene-1-octene copolymer, can use separately or two or more mixes and uses.
As above-mentioned polypropylene, except homopolymer, also having comprised copolymerization is the segmented copolymer or the random copolymers of the alpha-olefin of representative with ethene, and to have introduced in polymerization stage with the ethylene propylene rubber be the polypropylene of the rubber constituent of representative.Also have other operable new LDPE (film grade), polybutene, poly(4-methyl-1-pentene), ethene-butylene-hexene terpolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer etc. of also comprising.
In the present invention, above-mentioned (A) rubber and (B) crystalline polyolefin be that the cooperation ratio of resin is, total 100 weight parts with respect to both (A) account for 40～80 weight parts, (B) accounts for 60～20 weight parts.If rubber constituent surpasses 80 weight parts, then extrusion moulding significantly reduces.And,, then can't obtain good pliability if rubber constituent is less than 40 weight parts.
(C) metal hydroxides of Shi Yonging is to be used for giving composition with flame retardant resistance in the present invention, can promote simultaneously the crosslinked of rubber that silane compound graft copolymerization forms, and is crosslinked to carry out in the process of mixing.
Not fully aware of about promoting crosslinked mechanism, but be speculated as the dehydrating condensation that alkalescence that metal hydroxides has has promoted silanol group.
As such metal hydroxides, can enumerate magnesium hydroxide, aluminium hydroxide, calcium hydroxide etc., the wherein preferred best magnesium hydroxide of flame retardant effect.Metal hydroxides considers preferably to carry out surface treatment from dispersed angle.
As surface treatment agent, can use silane series coupling agent, titanate is coupling agent, lipid acid or fatty acid metal salt etc., is coupling agent from the angle consideration preferred silane that improves resin and the adaptation of metal hydroxides wherein.
As operable silane series coupling agent, can enumerate vinyl silane compounds such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane; Gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, β-(amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, N-phenyl-amino silane compounds such as gamma-amino propyl trimethoxy silicane; β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy silane compounds such as glycidoxy propyl group methyldiethoxysilane; Silicon Acrylote hydride compounds such as γ-methacryloxypropyl trimethoxy silane; Polysulfide silanes compounds such as two (3-(triethoxysilyl) propyl group) disulphide, two (3-(triethoxysilyl) propyl group) tetrasulfide; Hydrosulphonyl silane compounds such as 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane.
Handle the method for metal hydroxidess with these surface treatment agents, can use wet method, dry method, the direct known method such as method of mixing.
Being not particularly limited for treatment capacity, preferably is the scope of 0.1～5wt% with respect to metal hydroxides, if treatment capacity less than 0.1wt%, the strength degradation of resin combination then is if surpass 5wt%, then processibility variation.
And the median size of metal hydroxides is considered from the angle of mechanical characteristics, dispersiveness, flame retardant resistance, is preferably smaller or equal to 4 μ m.
(C) addition of metal hydroxides is that total 100 weight parts of resin are 40～250 weight parts with respect to (A) rubber and (B) crystalline polyolefin.If less than 40 weight parts, then can't obtain the excellent fire retardant effect, if surpass 250 weight parts, then pliability and physical strength significantly descend.
In the present invention, can (A) rubber or (B) crystalline polyolefin be the part of resin, rubber or crystalline polyolefin that the copolymerization of unsaturated carboxylic acid or derivatives thereof is formed are resin.Promptly can use (C) metal hydroxides and rubber or crystalline polyolefin that the copolymerization of unsaturated carboxylic acid or derivatives thereof is formed is resin.Thus, (C) react between metal hydroxides and the unsaturated carboxylic acid or derivatives thereof, improve adaptation, thereby improve the physical strength of composition.Here, rubber or crystalline polyolefin can directly use material recited above.
Be not particularly limited preferred maleic anhydride for the unsaturated carboxylic acid or derivatives thereof.In addition, can any amount replace preferred 0.5 weight part～10 weight parts.If be less than 0.5 weight part, the effect of the intensity that then can't be improved, if surpass 10 weight parts, then processibility significantly descends.
In addition, in the present invention, be used for promoting that the silanol condensation catalyst of crosslinked with silicane is not necessary, but also can add.Can further improve the degree of crosslinking of composition by interpolation, and composition of the present invention afterwards also can keep thermoplasticity.This moment, required moisture was to be supplied with by metal hydroxides or atmosphere.Also can on one's own initiative composition be exposed in the water vapour atmosphere about 80 ℃.
Operable catalyzer comprises dibutyltin dilaurate, dibutyl tin diacetate, dibutyl tin dicaprylate, stannous acetate, stannous octoate, zinc octoate, lead naphthenate, cobalt naphthenate etc., its addition is different because of the kind of catalyzer, can be set at 0.001～0.1 weight part with respect to 100 parts by weight of rubber.
As addition means, except the method for direct interpolation, be pre-mixed the method for the use masterbatch in rubber or the resin in addition.
Except aforesaid method, can also add additives such as processing oil, processing aid, flame retardant, vulcanization accelerator, vulcanization accelerator additive, antioxidant, lubricant, phase solvent, stablizer, carbon black, tinting material as required.
The device of making the present composition is not particularly limited, and can use multipurpose plants such as kneader, Banbury agitator, cylinder, twin screw extruder.
As the method for graft copolymerization silane compound on rubber, under the situation of using organo-peroxide, can make composition according to following operation.
Comprise following two operations, rubber, silane compound, organo-peroxide promptly mix, carry out the operation of graft copolymerization, and mix rubber, crystalline polyolefin of limit is crosslinked with silicane is carried out on Synergist S-421 95 limits such as resin and metal hydroxides to rubber operation, these two operations can be carried out respectively, for example also can adopt twin screw extruder to finish, be not particularly limited by once extruding.
In addition, the order the when rubber that mixes, crystalline polyolefin are resin and metal hydroxides three compositions can be arbitrarily, comprises (1) mix earlier rubber and metal hydroxides, and the method for polyolefin-based resins is added in the back; (2) mix earlier rubber and polyolefine, the method for metal hydroxides is added in the back; (3) methods of all mixing together etc.
When having the silane compound of the functional group of containing sulphur for the grafting rubbers copolymerization that contains the diene composition in molecule, the manufacturing step of composition is as follows.
(1) mixes after rubber and crystalline polyolefin be resin, add silane compound and further mix, add metal hydroxides at last and mix.
(2) mix after rubber and crystalline polyolefin be resin and metal hydroxides, add silane compound and mix.
(3) with rubber, crystalline polyolefin be resin, metal hydroxides, and silane compound drop into together and mix.
With rubber be dispersed in imperceptibly crystalline polyolefin be in the resin after with rubber cross, suppress rubber again aggegation be the basic of manufacture method, but so long as the rubber of crosslinked with silicane can be dispersed in imperceptibly crystalline polyolefin be resin mutually in, then can use other manufacturing step.
Here, when using silanol condensation catalyst, preferred last the adding.In addition, Synergist S-421 95 such as antioxidant or tinting material can be in office when section adds.
Above-mentioned non-halogen flame-retardant thermoplastic elastomer composition can be applied to electric wire and cable as isolator and sheath body.Especially can be used in line cord or cabtyre cable etc. and need excellent flexual purposes.
Embodiment
Below, specifically describe embodiments of the invention.
For use organo-peroxide to the grafting rubbers copolymerization material of silane compound, at first preparing will be as ethylene-propylene-diene copolymer (ethylene content 61%), vinyltrimethoxy silane, the diisopropylbenzyl superoxide of raw material, ratio dipping with 100/1/0.1 weight part and 100/5/0.5 weight part mixes the material that obtains, 40mm forcing machine (L/D=24) with 200 ℃, extrude with about 5 minutes residence time, carry out graft reaction.
Then, each composition of proportioning shown in each example of table 1 is dropped in 32mm twin screw extruder (L/D=42), mix,, make the thing that mixes by the rubber that crosslinked silane compound graft copolymerization in the process of mixing forms.
Design temperature is 180 ℃, and the spiral revolution is 150rpm.Be made into tablet, make as cable and use material.In addition,, then be positioned in the container that has been full of water vapour 24 hours, carry out crosslinked at 80 ℃ about having added the situation of silanol condensation catalyst.
For having used rubber that contains the diene composition and material, then use the 75L kneader to make with silane compound of the functional group of containing sulphur.
According to cooperate forming shown in the table 2, first mixed rubber, crystalline polyolefin are Synergist S-421 95s such as resin, metal hydroxides and antioxidant, add silane compound then, and composition to 180 ℃ mixes.In ensuing operation, the composition that will mix is supplied in and is set at 180 ℃ forcing machine, earnestly extrudes, and makes tablet shape sample.
To be supplied in the 65mm forcing machine (L/D=24) that is heated to 180 ℃ according to the tablet that above-mentioned two kinds of preparation methods make, on cable core, extrude the sheath body of coating 1.5mm thickness, make cable.Employed cable core is, with three on the copper conductor of external diameter 2mm with the poly object of 0.8mm thickness coating, after medium twiddles, press and obtain with the kraft paper gummed tape volume.
For the cable of making according to above-mentioned steps with following method evaluation.
Mensuration is used as the pliability index of material based on the durometer hardness (type A) of JIS K 6253; In addition an end of the cable of length 200mm is fixed,, measured the deflection (for the sagging distance of horizontal plane) of this moment, estimate the pliability of cable at the load of the additional 10g of the other end.The big more explanation pliability of deflection is good more.With the deflection of the hardness of the polyvinyl chloride sheath body of identical shaped ethene cabtyre cable and cable as target value (hardness is smaller or equal to 90, and deflection is more than or equal to 35mm).
Physical strength, thermotolerance, oil-proofness, flame retardant resistance are to estimate for benchmark according to JIS C 3005.More than or equal to 10MPa, it is qualified that the fracture extensibility is decided to be more than or equal to 350% situation with tensile strength.
Thermotolerance is to adopt to add heat distortion test (75 ℃, load 10N) and estimate, and it is qualified to be decided to be smaller or equal to 10% situation with the thickness decrement.
Oil-proofness be with IRM902 oil as test oil, at 70 ℃, flood after 4 hours, it is qualified that the tensile strength surplus is decided to be more than or equal to 60% situation.
The flame retardant resistance evaluation is to carry out 60 degree inclination combustion tests, be determined to remove burning away the time behind the flame, will 60 seconds with interior flame-out naturally be decided to be qualified.
In addition, in order to confirm whether carry out crosslinked with silicane, the extraction material is 24 hours in 130 ℃ hot dimethylbenzene.If remaining insoluble polymer is arranged, then be judged as carried out crosslinked.Formability is that the outward appearance when leaning on extrusion moulding is judged.Micro organization is with after the cut film dyeing of ruthenium tetroxide to material, uses the porjection type electron microscope observation.
Table 1
| Project | Target value | Embodiment | Comparative example | Embodiment | Comparative example | ||||||||||||||
| 1 | 2 | 1 | 2 | 3 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 4 | 5 | |||
| Form | Ethylene-propylene-diene copolymer (ethylene content 61%) | - | - | - | - | 80 | - | - | - | - | - | - | - | - | - | - | - | - | |
| Silane grafted ethene-propylene diene copolymerized thing (silane amount 1.0%, ethylene content 61%) | 80 | 40 | 85 | 35 | - | 45 | 45 | 45 | 70 | 69.9 | 69.9 | - | - | - | - | - | - | ||
| Silane grafted ethene-propylene diene copolymerized thing (silane amount 5.0%, ethylene content 61%) | - | - | - | - | - | - | - | - | - | - | - | 50 | 50 | 60 | 60 | 60 | 60 | ||
| Maleic anhydride grafted ethene-propylene diene copolymerized thing (maleic anhydride modified amount 1.0wt%) | - | - | - | - | - | 5 | 5 | 5 | - | - | - | - | - | - | - | - | - | ||
| Maleic anhydride grafted ethene-propylene copolymer (maleic anhydride modified amount 1.0wt%) | - | - | - | - | - | - | - | - | - | 0.1 | 0.1 | 0.5 | 10 | - | - | - | - | ||
| Polypropylene (density 0.900, MI 2.5) straight chain shape new LDPE (film grade) (density 0.912, MI 2.5) ethene-1-octene copolymer (density 0.858, MI 0.5) | - 20 - | - 60 - | - 15 - | - 65 - | - 20 - | 25 25 - | 25 25 - | 25 25 - | 30 - - | 30 - - | 30 - - | - 49.5 - | - 40 - | - - 40 | - - 40 | - - 40 | - - 40 | ||
| Magnesium hydroxide (silane treatment, median size 0.3 μ m) magnesium hydroxide (silane treatment, median size 0.8 μ m) magnesium hydroxide (fatty acid treatment, median size 0.8 μ m) aluminium hydroxide (silane treatment, median size 0.8 μ m) | 70 - - - | 70 - - - | 70 - - - | 70 - - - | 70 - - - | - 100 - - | - - 100 - | - - - 100 | - 80 - - | - 80 - - | - 80 - - | - - 120 - | - - 120 - | 40 - - - | 250 - - - | 35 - - - | 260 - - - | ||
| Dibutyltin dilaurate | - | - | - | - | - | - | - | - | - | - | 0.05 | - | - | - | - | - | - | ||
| Four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| Characteristic | Hardness | Smaller or equal to 90 | 78 | 89 | Can't measure | 91 | 76 | 89 | 87 | 88 | 85 | 86 | 86 | 86 | 88 | 80 | 90 | 78 | 92 |
| Pliability: deflection (mm) | More than or equal to 35 | 51 | 38 | 33 | 53 | 38 | 40 | 38 | 44 | 42 | 42 | 43 | 41 | 49 | 35 | 53 | 32 | ||
| Tensile strength (MPa) | More than or equal to 10 | 10.7 | 14.2 | 14.9 | 7.6 | 12.2 | 10.3 | 11.8 | 11.3 | 12.5 | 13 | 12.7 | 14.6 | 14 | 10.2 | 13.1 | 9.4 | ||
| Elongation (%) | More than or equal to 350 | 560 | 520 | 530 | 840 | 460 | 560 | 450 | 540 | 480 | 470 | 500 | 390 | 530 | 370 | 520 | 350 | ||
| Add thermal distortion: thickness decrement (%) | Smaller or equal to 10 | 2.8 | 2.6 | 2.3 | 7.1 | 0.8 | 0.8 | 1 | 1.4 | 1.2 | 0.7 | 2.4 | 1.9 | 5.5 | 3.6 | 5.7 | 3.1 | ||
| Oil-proofness: the remaining rate (%) of tensile strength | More than or equal to 60 | 70 | 80 | 83 | 65 | 93 | 88 | 94 | 88 | 87 | 92 | 80 | 86 | 65 | 65 | 67 | 66 | ||
| 60 degree inclining experiments (judgement burns away the time (second)) | Qualified smaller or equal to 60 | 48 is qualified | 46 is qualified | 48 is qualified | 49 is qualified | 32 is qualified | 33 is qualified | 44 is qualified | 45 is qualified | 45 is qualified | 42 is qualified | 30 is qualified | 29 is qualified | 58 is qualified | 14 is qualified | ＞60 is defective | 12 is qualified | ||
| Whether have crosslinked (have: zero, do not have: *) | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Extrusion moulding | Qualified | Qualified | Qualified | Defective | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | |
Table 2
| Project | Target value | Embodiment | Comparative example | ||||||||||||||||
| 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 6 | 7 | 8 | 9 | 10 | |||
| Form | Ethylene-propylene-diene copolymer (ethylene content 58%) | 80 | 70 | 70 | 70 | 70 | 70 | 70 | 70 | 60 | 70 | 40 | 70 | 70 | 90 | 30 | 70 | 70 | |
| Maleic anhydride grafted ethene-propylene diene copolymerized thing (maleic anhydride modified amount 1.0wt%) | - | - | - | - | - | - | - | - | 10 | - | - | - | - | - | - | - | - | ||
| Polypropylene (density 0.900, MI 2.5) | - | - | - | - | - | 30 | 30 | - | - | - | - | - | - | - | - | - | - | ||
| Straight chain shape new LDPE (film grade) (density 0.912, MI 2.5) | 20 | 30 | 30 | - | - | - | - | 30 | 30 | - | - | - | 30 | 10 | - | - | - | ||
| Ethylene-vinyl acetate (vinyl acetate 12%, MI 2.5) | - | - | - | 30 | 30 | 30 | - | - | - | 30 | 60 | 30 | - | - | 70 | 30 | 30 | ||
| Magnesium hydroxide (silane treatment, median size 0.3 μ m) magnesium hydroxide (silane treatment, median size 0.8 μ m) magnesium hydroxide (fatty acid treatment, median size 0.8 μ m) aluminium hydroxide (silane treatment, median size 0.8 μ m) | 70 - - - | - 70 - - | - - 70 - | - 70 - - | - - - 70 | - 70 - - | - 70 - - | 70 - - - | 70 - - - | - 40 - - | - 70 - - | - 250 - - | - 70 - - | 70 - - - | - 70 - - | - 30 - - | - 270 - - | ||
| Two (3-(triethoxysilyl) propyl group) tetrasulfide | 0.5 | 1 | 1 | - | - | 1 | 1 | - | - | 1 | 1 | 1 | - | 1 | 1 | 1 | 1 | ||
| 3-sulfydryl propyl trimethoxy silicane | - | - | - | 1 | 1 | - | - | 5 | 5 | - | - | - | - | - | - | - | - | ||
| Zinc acetate | - | - | - | - | - | - | - | - | - | 5 | 5 | 5 | - | - | 5 | 5 | 5 | ||
| Dibutyltin dilaurate | - | - | - | - | - | - | 0.05 | - | - | - | - | - | - | - | - | - | - | ||
| Four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| Characteristic | Hardness | Smaller or equal to 90 | 74 | 82 | 80 | 80 | 80 | 87 | 88 | 86 | 85 | 77 | 89 | 89 | 80 | Can't measure | 95 | 73 | 92 |
| Pliability: deflection (mm) | More than or equal to 35 | 50 | 40 | 45 | 42 | 42 | 34 | 35 | 44 | 42 | 48 | 36 | 35 | 45 | 30 | 50 | 31 | ||
| Tensile strength (MPa) | More than or equal to 10 | 11 | 13 | 10.3 | 11.2 | 11.5 | 12 | 14.3 | 12 | 14 | 13.1 | 14.5 | 10.1 | 7.6 | 14.8 | 14.9 | 8.8 | ||
| Elongation (%) | More than or equal to 350 | 550 | 490 | 560 | 500 | 520 | 500 | 400 | 410 | 380 | 600 | 510 | 360 | 820 | 480 | 620 | 340 | ||
| Add thermal distortion: thickness decrement (%) | Smaller or equal to 10 | 2.5 | 1.5 | 3 | 2.4 | 2 | 2.2 | 1 | 1.5 | 0.5 | 6.2 | 1.1 | 3.5 | 2.3 | 1 | 7.5 | 1 | ||
| Oil-proofness: the remaining rate (%) of tensile strength | More than or equal to 60 | 70 | 89 | 72 | 84 | 85 | 80 | 90 | 86 | 90 | 80 | 80 | 81 | 54 | 94 | 80 | 77 | ||
| 60 degree inclining experiments (judgement burns away the time (second)) | Qualified smaller or equal to 60 | 30 is qualified | 30 is qualified | 35 is qualified | 25 is qualified | 45 is qualified | 42 is qualified | 40 is qualified | 35 is qualified | 35 is qualified | 50 is qualified | 20 is qualified | 5 is qualified | 35 is qualified | 20 is qualified | ＞60 is defective | 5 is qualified | ||
| Whether have crosslinked (have: zero, do not have: *) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | ○ | |
| Extrusion moulding | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Defective | Qualified | Qualified | Qualified | |
Shown in table 1,2, embodiments of the invention 1～24 all have the pliability equal with polyvinyl chloride, and physical strength, thermotolerance, oil-proofness, flame retardant resistance, formability excellence.
In addition, confirmed that embodiment 1～24 has that rubber phase is dispersed in crystalline polyolefin is the micro organization of resin in mutually.
Comparing embodiment 3,4 or 14,15 can be known, has carried out silane coupling agent surface-treated metal hydroxides with using, and can obtain higher tensile strength.Comparing embodiment 3～5 or 16,17 can be known, by using magnesium hydroxide as metal hydroxides, can obtain more excellent flame.And then comparing embodiment 6,7 and 9,10 or 20,21 can know, by and with graft copolymerization as the ethylene-propylene-diene copolymer of the maleic anhydride of unsaturated carboxylic acid, can improve tensile strength.Comparing embodiment 7,8 or 18,19 can know, by adding dibutyltin dilaurate, the amount of remaining insoluble polymer increases to some extent, improved tensile strength, adds thermal distortion, the characteristic of cross-linking reaction degree such as oil-proofness.
Therefore on the other hand, in the comparative example 1 and 7, the ratio of rubber has demonstrated and has been dispersed with the tissue that crystalline polyolefin is a resin in the crosslinked rubber phase more than prescribed value, and extruding outward appearance becomes concavo-convexly, can't measure its characteristic.At the few comparative example 2 and 8 of rubber ratio, can't obtain sufficient pliability.In addition, rubber does not contain silane compound in the comparative example 3 and 6, and crosslinking reaction does not take place, so tensile strength is little, and adds thermal distortion and can't satisfy target value yet.Addition at metal hydroxides is lower than in the comparative example 4 and 9 of specified amount, and flame retardant resistance is insufficient, and in surpassing the comparative example 5 and 10 of specified amount, pliability and tensile strength are insufficient.
As mentioned above, the electric wire and the cable that use non-halogen flame-retardant thermoplastic elastomer composition of the present invention and use said composition, pliability and excellent in flame retardance, and have higher physical strength, thermotolerance, oil-proofness, its industrial value is high.
Claims (9)
1. non-halogen flame-retardant thermoplastic elastomer composition, it is characterized by, containing (A) rubber 40～80 weight parts, (B) crystalline polyolefin and be resin 60～20 weight parts, (C) is the metal hydroxides of 40～250 weight parts with respect to (A) with (B) total 100 weight parts, and this rubber has carried out crosslinked with silicane.
2. non-halogen flame-retardant thermoplastic elastomer composition according to claim 1 is characterized by, above-mentioned (A) rubber be dispersed in mutually (B) crystalline polyolefin be resin mutually in.
3. non-halogen flame-retardant thermoplastic elastomer composition according to claim 1 and 2 is characterized by, and above-mentioned (A) rubber is ethylene, propylene-diene copolymers.
4. according to each the described non-halogen flame-retardant thermoplastic elastomer composition in the claim 1～3, it is characterized by, above-mentioned (B) crystalline polyolefin is that resin is to be selected from least a in polypropylene, high density polyethylene(HDPE), straight chain shape new LDPE (film grade), ultra-low density polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, the ethene-1-octene copolymer.
5. according to each the described non-halogen flame-retardant thermoplastic elastomer composition in the claim 1～4, it is characterized by, above-mentioned (C) metal hydroxides is a magnesium hydroxide, and has carried out surface treatment by silane series coupling agent.
6. according to each the described non-halogen flame-retardant thermoplastic elastomer composition in the claim 1～5, it is characterized by, it is resin that above-mentioned composition contains rubber or crystalline polyolefin that the copolymerization of unsaturated carboxylic acid or derivatives thereof is formed.
7. make the method for each the described non-halogen flame-retardant thermoplastic elastomer composition in the claim 1～6, it is characterized by, the above-mentioned rubber that carries out crosslinked with silicane forms by rubber that silane compound graft copolymerization forms and metal hydroxides are mixed.
8. the manufacture method of non-halogen flame-retardant thermoplastic elastomer composition according to claim 7 is characterized by, and above-mentioned composition contains silanol condensation catalyst, by contacting with moisture, makes rubber cross.
9. electric wire and cable is characterized by, and each the described non-halogen flame-retardant thermoplastic elastomer composition in the claim 1～6 is used for isolator or sheath body.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101928440A (en) * | 2009-06-19 | 2010-12-29 | 日立电线株式会社 | Its electric wire, cable of non-halogen fire retardant resin composition and manufacture method thereof and use |
| CN101323689B (en) * | 2007-06-13 | 2011-04-13 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
| CN102969051A (en) * | 2011-08-29 | 2013-03-13 | 日立电线株式会社 | Coated wire and method of manufacturing the same |
| TWI424014B (en) * | 2011-11-08 | 2014-01-21 | Kenner Material & System Co Ltd | Thermal conductive and flame-retardant compositions |
| WO2015054893A1 (en) * | 2013-10-18 | 2015-04-23 | Dow Global Technologies Llc | Optical fiber cable components |
| CN106397997A (en) * | 2016-08-31 | 2017-02-15 | 宁波国海电子有限公司 | Halogen-free thermoplastic elastomer cable material and preparation method thereof |
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- 2006-08-09 CN CNB2006101154394A patent/CN100560646C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101323689B (en) * | 2007-06-13 | 2011-04-13 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
| CN101928440A (en) * | 2009-06-19 | 2010-12-29 | 日立电线株式会社 | Its electric wire, cable of non-halogen fire retardant resin composition and manufacture method thereof and use |
| CN101928440B (en) * | 2009-06-19 | 2014-04-02 | 日立电线株式会社 | Halogen-free flame resistance resin composition, manufacture method thereof, and wire and cable using halogen-free flame resistance resin composition |
| CN102969051A (en) * | 2011-08-29 | 2013-03-13 | 日立电线株式会社 | Coated wire and method of manufacturing the same |
| TWI424014B (en) * | 2011-11-08 | 2014-01-21 | Kenner Material & System Co Ltd | Thermal conductive and flame-retardant compositions |
| WO2015054893A1 (en) * | 2013-10-18 | 2015-04-23 | Dow Global Technologies Llc | Optical fiber cable components |
| CN105612449A (en) * | 2013-10-18 | 2016-05-25 | 陶氏环球技术有限责任公司 | Optical fiber cable components |
| US9670345B2 (en) | 2013-10-18 | 2017-06-06 | Dow Global Technologies Llc | Optical fiber cable components |
| EP3058408B1 (en) * | 2013-10-18 | 2019-11-20 | Dow Global Technologies LLC | Optical fiber cable components |
| CN106397997A (en) * | 2016-08-31 | 2017-02-15 | 宁波国海电子有限公司 | Halogen-free thermoplastic elastomer cable material and preparation method thereof |
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