CN101211681B - Fireproof electric wire and cable - Google Patents
Fireproof electric wire and cable Download PDFInfo
- Publication number
- CN101211681B CN101211681B CN2006101717854A CN200610171785A CN101211681B CN 101211681 B CN101211681 B CN 101211681B CN 2006101717854 A CN2006101717854 A CN 2006101717854A CN 200610171785 A CN200610171785 A CN 200610171785A CN 101211681 B CN101211681 B CN 101211681B
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- Prior art keywords
- functional group
- electric wire
- cable
- reactive functional
- organic
- Prior art date
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001446 poly(acrylic acid-co-maleic acid) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a fireproof wire cable, which comprises a conductor centre yarn and an organic/inorganic fireproof composite material as an insulation layer or coating layer of the wire cable. The organic/inorganic fireproof composite material comprises the following parts: an organic ingredient which has a first reaction functional group, wherein the organic ingredient comprises an organic macromolecule, a multipolymer, or a low polymer; and an inorganic powder which has a second reaction functional group. The organic ingredient and the inorganic powder form a chemical bonding through the first and the second reaction functional groups.
Description
Technical field
The present invention relates to a kind of fire-resistant wires/cable with environment-friendly fireproof insulating barrier and/or outer covering layer.
Background technology
Because economy of taiwan is grown up fast in recent years, it is also flourish to drive the construction industry, and incident is lifting for the building ' s fire idea.Statistics according to Fire Department of the Ministry of Internal Affairs, 93 years Taiwans of the Republic of China take place 6 altogether, 611 fire incidents, than 8 of the Republic of China 92 years, 642 with 88 years 18,254 have all been reduced sizable amplitude, and this optimum phenomenon and the recent compatriots idea of preventing fires promotes relevant with generally using gradually of building fireproofing installation.But because of the loss that fire caused, 93 years death tolls are up to 160 people with regard to China, and the damage to property that is caused shows that more up to 2,000,000,000 8 thousand 592 ten thousand 4 thousand yuan the loss that fire caused is still quite serious.Therefore, except the building dealer needs to do the more effective space planning with regard to fire prevention escape safety, most important fire Countermeasure promptly is the use of fireproofing flame-resistant fire proofing.At construction material, finishing (decorations) material, indoor and outdoor use electric wire and at home in the selection with its material essence such as article, flammable material should reduce use as far as possible, have flame proof, anti-flammability and flame resistance fire proofing material and need to use, enlarge fast in order to avoid burning things which may cause a fire disaster produces after-combustion, cause disaster to get out of hand.And along with depth of building and density fast lifting, fire produces the source and spreads the factor and increases, and personnel's fire-fighting life-saving is more difficult, so its application of employed fireproofing flame-resistant fire proofing also needs to promote with use aspect and fire resistance property thereupon.
Among the fireproofing flame-resistant fire proofing, indoor and outdoor use flame-retardant electric wire and cable is a considerable problem.Electric wire is that media is transmitted in the transmission of electric energy, use quite extensive, fields such as building construction, public work, telecommunications, electronics, motor and information are used all very general, just because of a large amount of uses of electric wire, to cause propagation of flame to lead to the accident of fire disaster of common occurrence especially owing to electric wire cocks off, in order to prevent that this type of accident from constantly taking place, the anti-flammability of electric wire must promote.The insulating barrier of existing electric wire with cover (lining) layer material outward quite a lot of kind arranged, mainly can be divided into thermoplasticity and thermosetting two classes.Thermoplasticity has PVC, LDPE, HDPE, PP, PU, nylon and Teflon etc., thermosetting then has SBR, NBR, EPR, EPT and silicon rubber kinds such as (silicone rubber), that uses maximum in these materials is polyvinyl chloride (PVC) and polyolefin (polyolefin) or its copolymer, wherein is (table 1) with PE again.PE volume resistance high (〉 1017 Ω-cm), insulating properties and engineering properties are good, but the flame resistance extreme difference is a kind of very easily material of combustion, can add the incombustible agent of halogen system, phosphorus system or inorganic system for the flame resistance matter that promotes PE.And PVC volume resistance height (1013-1015 Ω-cm), insulating properties and engineering properties are also quite good, and anti-flammability than other material such as PE come good, so be used to replace PE as the flame retardant insulation of various electric wires with cover (lining) layer outward.Yet because halogen is the composition that incombustible agent and PVC contain bromine and chlorine, though halogenic ingredient can promote the anti-flammability of material, but meeting toxigenicity gas after the burning, cause sizable harm for environment and people's cognition, and the RoHS of European Union in 2006 (Restriction on the use of certain Hazardous) rules, forbidding PBBs, the plastic material of the halogen-containing incombustible agent of PBDEs, countries in the world are also for the material of halogen-containing composition increasing standard in addition, so under this trend, containing in the future the disruptive halogen of environment is that material use restriction must be more and more harsh, and halogen is that the use of incombustible agent and PVC must be more and more limited.Therefore, electric wire is that environmental-protection flame-retardant covers (lining) layer material outward at the emphasis that becomes the electric wire research and development gradually and produce in recent years with non-halogen.
Table 1, general power line PE and PVC characteristic comparison sheet
With existing electric wire flame retardant insulation with cover (lining) layer material outward, owing to PVC has splendid flame-retardant nature, so PVC is the most extensive material that is used.As Japan Patent JP10330569, JP7211153, Korean Patent KR9201723B and European patent EP 0029234 etc., all directly use PVC add plasticiser (plasticizer) and stabilization agent (stabilizer) as the flame retardant insulation of electric wire with cover (lining) layer outward; NZ207294 then with crosslinked PVC coat uncrosslinked PVC as the flame retardant insulation of electric wire with cover (lining) layer outward.In addition, PVC also often arranges in pairs or groups the additive of other organic or inorganic with its anti-flammability of further lifting, adds calcium salt, zinc salt, magnesium salts and aluminium salt etc. as EP0769789 with PVC; US5891571 adds phosphate and the anti-flammability of halo plasticiser (halogenatedplasticizer), aluminium hydroxide, antimonous oxide and zinc additives such as (zinc stannate) with lifting PVC with PVC; PVC also can arrange in pairs or groups other polyolefin macromolecule promoting its water preventing ability, as JP1041112 be with the copolymer of ethene-PVC and ethylene-vinyl acetic acid esters-PVC as the flame retardant insulation of electric wire with cover (lining) layer outward.
Yet the electric insulating quality of PVC is relatively poor, and the electric wire that many high voltages are used is comparatively harsh for the demand of its electric insulating quality.So wire cable insulating layer and the selection of covering (lining) layer material outward, can with the preferable polyolefin series macromolecule of electric insulating quality as the insulating barrier of cable with cover (lining) layer outward, or cover (lining) layer outward as the insulating barrier PVC that arranges in pairs or groups with polyolefin.With the polyolefin series macromolecule as the insulating barrier of cable with cover (lining) layer outward, the anti-flammability that how to promote very inflammable polyolefin series macromolecular material is a very important problem.Most polyolefin series macromolecules can adopt the mode of adding fire-retardant/incombustible agent to improve the high molecular anti-flammability of polyolefin series, are to add materials such as metal hydroxides, silane, siloxanes in polyolefin such as PE, PP as patents such as US6303681 (B1), US5166250, JP2000191845 and CA2210057; Patent US20060148939 then adds inorganic constituents in macromolecules such as PE, PP, EPR, EPDM, EVA, as SiC, CaO, SiO
2Deng powder, and the second fire-retardant additive of arranging in pairs or groups, as organic or Phos based compound, antimony containing compounds and metal hydroxides etc.; Patent JP2005322474 adopts the copolymer with organic substance such as EVA or styrene-ethylene-butylene (styrene-ethylene-butylene) to add Mg (OH)
2And the mode of silane coupling agent, promote its fire retardancy; Patent US20050205290 adds nature of glass additive in organic polymer HDPE, MDPE and LDPE, as phosphorous glasses matter additive B
2O
3, P
2O
5, PbO etc., and arrange in pairs or groups dystectic silicate or hydroxide are to promote multiple material fire retardancy.
Above-mentioned before the case patent except direct uses PVC as the electric wire flame retardant insulation and cover outside (lining) layer material, general inflammable macromolecular material all be do not fire to add, the inorganic system additive of high-melting-point, high cracking temperature, and the hydroxide that can discharge aqueous vapor, reach the purpose that promotes anti-flammability in the mode that blendes together with organic polymer, there is no direct reaction between its fire-retardant additive and the organic polymer and produce chemical bonded refractory.Therefore under the influence of flame and heat, can produce fusing, fusion or drip phenomenon such as hang down,, that is can't protect other combustible material not ignited under flame and the heat and effectively delay propagation of flame having so the difficult characteristic of firing is not sufficient to provide fire resistance property.
Summary of the invention
In view of this, the present invention uses different fire-retardant notions, and not using halogen is incombustible agent and PVC, but selects for use the organic principle with reactive functional group to react with the inorganic particle with corresponding reactive functional group base, forms organic/inorganic composite material.This organic/inorganic composite material can be according to the suitable procedure for processing of the difference of use organic principle system collocation, with extrusion (extrusion) or impregnation modes such as (dipping) be processed into electric wire insulating barrier or/and cover (lining) layer (outer sheath) outward.
Fireproof electric wire and cable of the present invention comprises: conductor core wire, and organic/inorganic Flameproof composite material, and as the insulating barrier or the outer covering layer of this electric wire.Above-mentioned organic/inorganic Flameproof composite material comprises: organic principle, have first reactive functional group, and this organic principle comprises: organic polymer, copolymer or oligomer; And inorganic particle, have second reactive functional group; Wherein organic principle and inorganic particle form chemical bonded refractory via first and second reactive functional group.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and cooperate appended graphicly, be described in detail below:
Description of drawings
Fig. 1 illustrates the impregnation coating schematic diagram of the fire prevention outer covering layer of embodiment 1.
The primary clustering symbol description
100～copper cash;
200～slurry;
300～outer covering layer;
400～container.
Embodiment
Utilization of the present invention itself has reactive functional group, or can be via the inorganic powder material that possesses surface functionalities behind surface treatment, the upgrading, produce reaction with the reactive functional group of organic polymer, monomer, oligomer or prepolymer, and it is scattered in the organic principle system equably, is reprocessed into to the insulating barrier of electric wire or/and covers (lining) layer outward.Owing to have chemical bonded refractory because of reaction between organic principle in flame retardant insulation and the outer covering layer material and the inorganic particle, this flame retardant insulation and outer covering layer are when having flame combustion or contacting a large amount of heat, organic principle in flame retardant insulation and the outer covering layer can't melt or burn and causes propagation of flame and transfer, and can form the hard coke layer of structure by flash carbonization, inorganic powder material and other additive then can at high temperature produce the effect of radiation heat release, flame and heat that contact is transmitted are emitted in the mode of radiation, have the effect of dissipation heat.The fire-retardant mechanism of this kind can be under the prerequisite of not adding halogen-containing based compound or difficult combustion fire retardant, effectively stop spreading and transfer of flame and heat, also can not produce gas with toxicity or the material that forms because of halogen, be a kind of environmental-protection flame-retardant insulating barrier and cover (lining) layer outward.
In the above-mentioned organic/inorganic Flameproof composite material, the content of organic principle can be between 10-90wt%, and the content of inorganic particle can be between 90-10wt%; In preferred embodiment, organic component content is 30-70wt%, and inorganic particle content is 70-30wt%; In better embodiment, organic component content is 40-60wt%, and inorganic particle content is 60-40wt%.Be referred to as among the present invention " oligomer " mean about 200 to the 1499 daltonian compounds of number-average molecular weight, and " copolymer " with " organic polymer " mean that number-average molecular weight about 1500 is to greater than 1,00,000 daltonian compound.
The reactive functional group of organic principle and inorganic particle includes, but are not limited to :-OH ,-COOH ,-NCO ,-NH
3,-NH
2,-NH, epoxy radicals etc.For example, can select to have-COOH or-NCO functional group's organic principle (as organic acid based compound or reaction type polyurethane) with have-OH functional group's inorganic particle (as metal hydroxides) reaction.Organic principle and the surface that also can select to have epoxy radicals (epoxy) have-NH
2Functional group's inorganic particle reaction.Otherwise, also can select to have-OH functional group's organic principle (as polyvinyl alcohol) with have-COOH or-NCO functional group's inorganic particle reaction, perhaps select to have-NH
2Functional group's organic principle and inorganic particle reaction with epoxy radicals (epoxy).
Organic principle of the present invention comprises any the have oligomer of above-mentioned reactive functional group, single polymer or copolymer, and reactive functional group can be positioned at high polymer main chain or side chain, and the preferably comprises: poly-organic acid (polyorganic acid) is, polyurethane (polyurethane) is, epoxy (epoxy) is, polyolefin (polyolefin) is, polyamine (polyamine) is etc.Wherein, poly-organic acid system comprise have carboxylic acid, the single polymers or the copolymer of sulfonic acid, for example be: ethylene acrylic acid co polymer (poly (ethylene-co-acrylicacid)), acrylic acid maleic acid (poly (acrylic acid-co-maleic acid)) etc.Epoxy system for example is two (3,4-epoxy-6-methyl cyclohexane ylmethyl) [Bis (3 for adipate ester, 4-epoxy-6-methylcyclohexylmethyl) adipate], vinyl cyclohexene dioxide [Vinylcyclohexene dioxide], tetrahydrophthalic acid 2-glycidyl ester [Diglycidyl tetrahydrophthalate], hexahydro-phthalic acid 2-glycidyl ester [Diglycidyl hexahydrophthalate], two (2,3-epoxide ring amyl group) ether resin [Bis (2,3-epoxycyclopentyl) ether resin], the glycidol ether of polyphenol epoxy resin [Glycidyl ethers of polyphenol epoxy resin] etc.Polyamine system comprises polyamide (polyamide) and polyimides (polyimide), and polyamide for example is: nylon 6[nylon6 ((NH (CH
2)
5CO)
n)], nylon 66[nylon66 ((NH (CH
2)
6-NH-CO (CH
2)
4CO)
n)], nylon 12[nylon12 ((NH (CH
2)
11CO)
n)] etc.Polyimides system comprises diamines (diamine) and the polyimides that is synthesized with diamines and dianhydride (dianhydride), diamines for example is 4,4-oxydiphenyl amine [4,4-oxydianiline], 1,4 pairs of [(4-amino-benzene oxygen) benzene] [1,4-bis (4-aminophenoxy) benzene], 2, two [4-(4-amino-benzene oxygen) phenyl] propane [2 of 2-, 2-bis[4-(4-aminophenoxy) phenyl] propane] etc., and with above-mentioned diamines collocation dianhydride such as oxygen di-phthalic anhydride (oxydiphthalicanhydride), pyromellitic acid dianhydride (pyromellitic dianhydride), the polyimides that benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride) etc. is synthesized.Polyolefin comprises the copolymer of the monomer of olefinic monomer and above-mentioned tool reactive functional group.It should be noted that the starting material of organic principle still can comprise above-mentioned monomer, oligomer or prepolymer, in addition, more can simultaneously two or more organic principles be mixed and take use.
Inorganic constituents used in the present invention comprises the inorganic particle that itself has above-mentioned functional group, or via the inorganic particle that possesses above-mentioned functional group behind surface treatment, the upgrading.Preferable inorganic particle comprises: hydroxide, nitride, oxide, carbide, metallic salt or inorganic lamellar material etc.Wherein, hydroxide comprises metal hydroxides, as aluminium hydroxide (Al (OH)
3), magnesium hydroxide (Mg (OH)
2) etc.Nitride comprises boron nitride (BN), silicon nitride (Si
3N
4) etc.Oxide comprises silicon dioxide (SiO
2), titanium dioxide (TiO
2), zinc oxide (ZnO) etc.Carbide for example is carborundum (SiC).Metallic salt for example is calcium carbonate (CaCO
3).Inorganic lamellar material comprises two oxyhydroxide (the Layered Double Hydroxides of clay, talcum (talc) or stratiform; LDH) etc., wherein clay can be silicon aluminite class clay (smectite clay), vermiculite (vermiculite), halloysite (halloysite), sericite (sericite), bentonite (saponite), imvite (montmorillonite), beidellite (beidellite), nontronite (nontronite), mica (mica) and hectorite (hectorite) etc.It should be noted that above-mentioned inorganic constituents also can be mixed use, for example add clay and metal hydroxides simultaneously with reactive functional group.Inorganic particle can be micron particles or nano-scale particle, and is wherein preferable with the nano-scale particle of particle diameter 1～100nm again, because smaller particle size can improve the surface area of Unit Weight.
Organic principle can directly mix with inorganic particle and reacts, and perhaps reacts the formation covalent bond in the presence of all kinds of solvents (for example water, ethanol or methyl ethyl ketone).The temperature range of reaction is decided on employed composition, and generally between room temperature to 150 ℃, the reaction time can not waited from 10 minutes to a couple of days.
Demand in the above-mentioned visual practical application of organic/inorganic Flameproof composite material is added various additive, for example can further promote the material flame retardancy fire retardant (as Mei Naiming phosphate-based (MelaminePhosphates), red phosphorus and phosphorus flame retardant), strengthen structure and the glass sand of the silane (as TEOS, TEVS) assisting to solidify or siloxanes (siloxane), reinforcing material thermal endurance and structural strength or glass fibre etc.The amount of additive is generally at the 0.1-20 weight portion, and the organic/inorganic composite material of its 100 weight portion is a benchmark.
Organic/inorganic Flameproof composite material of the present invention can be according to the suitable procedure for processing of difference collocation of use organic principle system, with extrusion (extrusion) or impregnation modes such as (dipping) be processed into various electric wires insulating barrier or/and cover (lining) layer outward, for example power line, data line, communication are with electric wire and cable etc.Because between organic principle of the present invention and the inorganic particle is that chemical bonded refractory is arranged, do not have fusion when therefore meeting heat/flame, drip hang down, phenomenon such as burning, be different from the general physical blending.
Above-mentioned Flameproof composite material can pass through the test of VW-1 (UL1581) vertical combustion and need not other material directly as the insulating barrier of conductor core wire.In addition, also can be earlier be coated on conductor core wire (being generally aluminium or copper) surface as insulating barrier with Flameproof composite material, again with other material such as PVC as outer covering layer; Perhaps, also the material of available general no fire-retardant effect such as PE coating conductor heart yearn as insulating barrier after, imposing Flameproof composite material of the present invention outward again is outer covering layer, and with above-mentioned Flameproof composite material as outer covering layer, wherein outer covering layer can separate with insulating barrier and forms, or forms simultaneously in the mode of extrusion altogether.
Embodiment
Embodiment 1
The ethylene acrylic acid co polymer (acrylic acid content 15wt%) of 300.0g is placed reaction vessel, preheat to 110-120 ℃ its fusing back is stirred with 300rpm constant temperature constant speed.Stirring reaction presents white emulsion liquid after adding 324.0g deionized water and 324.0g ammoniacal liquor after 10 minutes, adds 300g aluminium hydroxide powder stirring reaction again and can obtain white uniform sizing material in 10 minutes.Please refer to Fig. 1, select for use 14AWG/3G bare copper wire 100 to be base material, with impregnation processing procedure (dipping) slurry in the container 400 200 is coated copper cash, formation thickness is 0.25mm, 0.53mm, the outer covering layer 300 of three kinds of different-thickness of 1.02mm.This coating sample is sent into baking oven carry out shaping and drying, program is as follows:
60℃(60min)→80℃(60min)→100℃(60min)→120℃(30min)→140℃(30min)→160℃(240min)
After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 2.Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since ethylene acrylic acid co polymer-COOH functional group and aluminium hydroxide (Al (OH)
3)-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 2 embodiment 1
Embodiment 2
The ethylene acrylic acid co polymer of 300.0g is placed reaction vessel, preheating to 110-120 ℃ makes its fusing back stir with 300rpm constant temperature constant speed, add 300.0g aluminium hydroxide powder stirring reaction and can obtain white uniform sizing material in 10 minutes, can solidify out into white bulk material after slurry is cooled to room temperature.White bulk material is pulverized the back as in the extruder (Extruder), select for use the 14AWG/3G bare copper wire in 130 ℃ of electric wire skins that carry out common extrusion (co-extrusion) preparation 0.2mm, 0.5mm, three kinds of different-thickness of 1.0mm.This extrusion sample is sent into baking oven carry out shaping and drying, program is as follows:
60℃(60min)→80℃(60min)→100℃℃(60min)→120℃(30min)→140℃(30min)→160℃(240min)
After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 3.Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since ethylene acrylic acid co polymer-COOH functional group and aluminium hydroxide (Al (OH)
3)-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 3 embodiment 2
Embodiment 3
The acrylic acid acid/maleic acid copolymers of 300.0g is placed reaction vessel, preheating to 110-120 ℃ makes its fusing back stir with 300rpm constant temperature constant speed, add 300.0g magnesium hydrate powder stirring reaction and can obtain white uniform sizing material in 10 minutes, can the little yellow bulk material of solidify out into after slurry is cooled to room temperature.Little yellow bulk material is pulverized the back as in the extruder, select for use the 14AWG/3G bare copper wire to carry out the electric wire skin that common extrusion prepares 0.2mm, 0.5mm, three kinds of different-thickness of 1.0mm in 130 ℃.This extrusion sample is sent into baking oven carry out shaping and drying, program is as follows:
60℃(60min)→80℃(60min)→100℃(60min)→120℃(30min)→140℃(30min)→160℃(240min)
After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 4.Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since the acrylic acid acid/maleic acid copolymers-COOH functional group and magnesium hydroxide (Mg (OH)
2)-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 4 embodiment 3
Embodiment 4
With 500.0g contain 8% reactive isocyanate (NCO) functional group's reaction type polyurethane (reactive polyurethane) places reaction vessel to stir with 300rpm room temperature constant speed, add the 500.0g aluminium hydroxide powder again after stirring reaction can obtain white uniform sizing material in 5 minutes.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 1.04mm, 2.15mm, 2.97mm.The impregnation processing procedure is adopted in the slurry coating.Sample was placed the room temperature compacted under dry 24 hours.After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 5.
Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since reaction type polyurethane-NCO functional group and aluminium hydroxide (Al (OH)
3)-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 5 embodiment 4
Embodiment 5
500.0g is contained 8% reactive isocyanate (after NCO) functional group's reaction type polyurethane adds 300.0g DMAC, place reaction vessel to stir with 300rpm room temperature constant speed, add the 500.0g aluminium hydroxide powder again after stirring reaction can obtain the low white uniform sizing material of viscosity in 5 minutes.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 0.21mm, 0.49mm, 0.98mm.The impregnation processing procedure is adopted in the slurry coating.Place the room temperature compacted under to move into 105 ℃ of oven drying moulding 24 hours in dry 24 hours again on this sample.After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result as shown in Table 6.
Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since reaction type polyurethane-NCO functional group and aluminium hydroxide (Al (OH)
3)-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 6 embodiment 5
Embodiment 6
500.0g is contained 8% reactive isocyanate, and (NCO) functional group's reaction type polyurethane places reaction vessel to stir with 300rpm room temperature constant speed, add again 450.0g magnesium hydrate powder and 50.0g through upgrading have-OH functional group's nano clay after, stirring reaction can obtain the low white uniform sizing material of viscosity in 5 minutes.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 1.10mm, 2.26mm, 2.95mm.The impregnation processing procedure is adopted in the slurry coating.This sample was placed the room temperature compacted under dry 24 hours.After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 7.
Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can not produce a vertical phenomenon, cover (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Thus embodiment as can be known since reaction type polyurethane-NCO functional group and magnesium hydroxide (Mg (OH)
2)-OH functional group and nano clay through upgrading had-the OH functional group produces reaction and forms bond, strengthened the outer structure of covering (lining) layer material, significantly promoted the flame-retarding characteristic that covers (lining) layer material outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 7 embodiment 6
Embodiment 7
500.0g is contained 7.6% reactive isocyanate, and (NCO) functional group's reaction type polyurethane places reaction vessel to stir with 300rpm room temperature constant speed, add again through upgrading have-OH functional group's 450.0g titanium dioxide powder and 50.0g through upgrading have-OH functional group's nano clay after, stirring reaction can obtain white uniform sizing material in 5 minutes.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 0.70mm, 1.46mm, 2.00mm.The impregnation processing procedure is adopted in the slurry coating.Place the room temperature compacted under to move into 80 ℃ of baking oven shaping and dryings again 24 hours in dry 24 hours on this sample.After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 8.
Covering in addition that (lining) layer is neither in first to the 5th combustion testing can burning, and flame can not spread to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce a vertical phenomenon, but the bottom cotton of can't igniting is covered (lining) layer material outward by the test of VW-1 (UL1581) vertical combustion.
Embodiment as can be known thus, owing to reaction type polyurethane-NCO functional group and titanium dioxide surface upgrading institute bond-OH functional group and nano clay through upgrading had-the OH functional group produces reaction and forms bond, strengthen the outer structure of covering (lining) layer material, significantly promoted the outer flame-retarding characteristic that covers (lining) layer material.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 8 embodiment 7
Comparative example 1
500.0g is contained 7.6% reactive isocyanate, and (NCO) functional group's reaction type polyurethane places reaction vessel to stir with 300rpm room temperature constant speed, adds 500.0g again and can obtain white uniform sizing material in 5 minutes without the silicon-dioxide powdery stirring reaction of surfaction.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 0.72mm, 1.31mm, 2.01mm.The impregnation processing procedure is adopted in the slurry coating.Place the room temperature compacted under to move into 80 ℃ of baking oven shaping and dryings again 24 hours in dry 24 hours on this sample, placed room temperature more following 72 hours.After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 9.
Cover in addition (lining) layer first or for the second time during combustion testing to produce burning, propagation of flame is to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce and drip vertical phenomenon and the bottom cotton of can igniting, cover (lining) layer material outward and can't pass through VW-1 (UL1581) vertical combustion and test.
Comparative example as can be known thus, owing to silica surface can't with reaction type polyurethane-the NCO functional group produces enough reactions and forms bond, the structure of covering (lining) layer material outward is the efficient hardening via the reaction of organic/inorganic not, so cover (lining) layer material and there is no significant flame-retarding characteristic outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 9 comparative example 1
Comparative example 2
500.0g is not contained reactive isocyanate, and (NCO) functional group's polyurethane places reaction vessel to stir with 300rpm room temperature constant speed, adds aluminium hydroxide powder 500.0g again, and stirring reaction can obtain white uniform sizing material after 5 minutes.Selecting the 14AWG/3G bare copper wire for use is base material, and slurry is coated the copper cash skin, and thickness is three kinds of 0.52mm, 1.17mm, 1.88mm.The impregnation processing procedure is adopted in the slurry coating.This coating sample is sent into baking oven carry out shaping and drying, program is as follows:
60℃(120min)→80℃(120min)→100℃(120min)→120℃(360min)
After treating the complete forming and hardening of cladding material, carry out the test of VW-1 (UL1581) vertical combustion, test result is as shown in table 10.
Cover in addition (lining) layer first or for the second time during combustion testing to produce burning, propagation of flame is to the flag on specimen top.Cover (lining) layer material during combustion testing outward and can produce and drip vertical phenomenon and the bottom cotton of can igniting, cover (lining) layer material outward and can't pass through VW-1 (UL1581) vertical combustion and test.
Comparative example as can be known thus, because polyurethane anergy functional group, can't with aluminium hydroxide-the OH functional group produces enough reactions and forms bond, the structure of covering (lining) layer material outward is the efficient hardening via the reaction of organic/inorganic not, so cover (lining) layer material and there is no significant flame-retarding characteristic outward.
Electric wire sample VW-1 (UL1581) the vertical combustion test result of table 10 comparative example 2
Though the present invention discloses as above with several preferred embodiments; right its is not in order to limit the present invention; have in the technical field under any and know the knowledgeable usually; without departing from the spirit and scope of the present invention; when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking appended the claim person of defining.
Claims (18)
1. fireproof electric wire and cable comprises:
Conductor core wire;
The organic/inorganic Flameproof composite material, as the insulating barrier or the outer covering layer of this electric wire, wherein this organic/inorganic Flameproof composite material comprises:
Organic principle has first reactive functional group that is selected from NCO, epoxy radicals, hydroxyl or amido, and this organic principle comprises: organic polymer, copolymer or oligomer; And
Inorganic particle has second reactive functional group that is selected from hydroxyl, amido, carboxyl, NCO or epoxy radicals;
Wherein this organic principle and this inorganic particle form chemical bond via this first and second reactive functional group; Wherein
(a) when this first reactive functional group is NCO, this second reactive functional group is a hydroxyl;
(b) when this first reactive functional group is epoxy radicals, this second reactive functional group is an amido;
(c) when this first reactive functional group is hydroxyl, this second reactive functional group is carboxyl or NCO; And
(d) when this first reactive functional group is amido, this second reactive functional group is an epoxy radicals.
2. fireproof electric wire and cable as claimed in claim 1, wherein this organic component content is 10-90 weight % in this organic/inorganic Flameproof composite material, this inorganic particle content is 90-10 weight %.
3. fireproof electric wire and cable as claimed in claim 1, wherein this organic component content is 30-70 weight % in this organic/inorganic Flameproof composite material, this inorganic particle content is 70-30 weight %.
4. fireproof electric wire and cable as claimed in claim 1, wherein this organic principle comprises: poly-organic acid system, polyurethane series, epoxy system, polyolefin or polyamine system.
5. fireproof electric wire and cable as claimed in claim 1, wherein this inorganic particle comprises: hydroxide, nitride, oxide, carbide, metallic salt or inorganic lamellar material.
6. fireproof electric wire and cable as claimed in claim 5, wherein this hydroxide comprises metal hydroxides.
7. fireproof electric wire and cable as claimed in claim 6, wherein this metal hydroxides comprises aluminium hydroxide or magnesium hydroxide.
8. fireproof electric wire and cable as claimed in claim 5, wherein this nitride comprises boron nitride or silicon nitride.
9. fireproof electric wire and cable as claimed in claim 5, wherein this oxide comprises silicon dioxide, titanium dioxide or zinc oxide.
10. fireproof electric wire and cable as claimed in claim 5, wherein this carbide comprises carborundum.
11. fireproof electric wire and cable as claimed in claim 5, wherein this metallic salt comprises calcium carbonate.
12. fireproof electric wire and cable as claimed in claim 5, wherein this inorganic lamellar material comprises the two oxyhydroxides of clay, talcum or stratiform.
13. fireproof electric wire and cable as claimed in claim 1, wherein this organic/inorganic Flameproof composite material system is coated on this conductor core wire with extrusion or impregnation mode.
14. fireproof electric wire and cable as claimed in claim 1, wherein this fireproof electric wire and cable is by the test of VW-1 (UL 1581) vertical combustion.
15. fireproof electric wire and cable as claimed in claim 1, wherein this first reactive functional group is a NCO, and this second reactive functional group is a hydroxyl.
16. fireproof electric wire and cable as claimed in claim 1, wherein this first reactive functional group is an epoxy radicals, and this second reactive functional group is an amido.
17. fireproof electric wire and cable as claimed in claim 1, wherein this first reactive functional group is a hydroxyl, and this second reactive functional group is carboxyl or NCO.
18. fireproof electric wire and cable as claimed in claim 1, wherein this first reactive functional group is an amido, and this second reactive functional group is an epoxy radicals.
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| CN2006101717854A CN101211681B (en) | 2006-12-29 | 2006-12-29 | Fireproof electric wire and cable |
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| CN2006101717854A CN101211681B (en) | 2006-12-29 | 2006-12-29 | Fireproof electric wire and cable |
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| CN101211681B true CN101211681B (en) | 2010-09-15 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102682907A (en) * | 2012-05-08 | 2012-09-19 | 江苏珠影特种电缆有限公司 | Fireproof high-temperature-resistant power cable |
| CN103254531A (en) * | 2013-05-27 | 2013-08-21 | 常州大学 | Flame-retardant PVC (polyvinyl chloride) composite material and preparation method thereof |
| CN103319922A (en) * | 2013-05-31 | 2013-09-25 | 镇江天信电器有限公司 | Novel insulating paint |
| CN104778995A (en) * | 2015-04-01 | 2015-07-15 | 苏州欢颜电气有限公司 | Enameled wire and preparation method thereof |
| CN105489299A (en) * | 2016-01-25 | 2016-04-13 | 中天科技装备电缆有限公司 | High-flame-retardation high-fireproof flexible cable used for communication power supply |
| CN107293367A (en) * | 2016-02-25 | 2017-10-24 | 杨攀 | A kind of durable power cable |
| CN109054867B (en) * | 2018-08-21 | 2020-12-15 | 阜阳创启工艺品有限公司 | Environment-friendly fire-resistant flame-retardant bag for cable well |
| CN110308039A (en) * | 2019-05-30 | 2019-10-08 | 常州金标轨道交通技术服务有限公司 | Cable for rail transit vehicles all-round property testing method |
| JP2023047361A (en) * | 2021-09-27 | 2023-04-06 | 東特塗料株式会社 | electric insulated wire |
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| CN1052211A (en) * | 1989-12-02 | 1991-06-12 | 新都电缆厂 | Speical flame retardant cable |
| CN1077050A (en) * | 1992-03-06 | 1993-10-06 | 美国电话电报公司 | Propagation of flame and smog are formed the cable with super resistance |
| CN1341141A (en) * | 1999-12-23 | 2002-03-20 | 巴塞尔技术有限公司 | Flame-proof polyolefin compositions |
| CN1563165A (en) * | 2004-03-25 | 2005-01-12 | 上海交通大学 | Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method |
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|---|---|---|---|---|
| CN1052211A (en) * | 1989-12-02 | 1991-06-12 | 新都电缆厂 | Speical flame retardant cable |
| CN1077050A (en) * | 1992-03-06 | 1993-10-06 | 美国电话电报公司 | Propagation of flame and smog are formed the cable with super resistance |
| CN1341141A (en) * | 1999-12-23 | 2002-03-20 | 巴塞尔技术有限公司 | Flame-proof polyolefin compositions |
| CN1563165A (en) * | 2004-03-25 | 2005-01-12 | 上海交通大学 | Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method |
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