CN102858873B - Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same - Google Patents
Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same Download PDFInfo
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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Abstract
Provided is a non-halogen flame-retardant resin composition which exhibits excellent mechanical strengths (such as flexibility and wear resistance), excellent flame retardance, particularly excellent cut-through characteristics, and tensile elongation characteristics satisfying the UL standards. Also provided are an electric wire and a cable which are made using the resin composition as a cover layer. A non-halogen flame-retardant resin composition which comprises 100 parts by mass of a resin component and 5 to 40 parts by mass of a phosphorus-based flame retardant, wherein the resin component comprises 30 to 85 parts by mass of a polyolefin resin, 10 to 50 parts by mass of a polyphenylene ether resin, and 5 to 30 parts by mass of a styrene-based elastomer, each content (parts by mass) being relative to 100 parts by mass of the resin component, and the polyolefin resin comprises 5 to 60% by mass of an ethylene/propylene random copolymer obtained by polymerization using a metallocene catalyst and 30 to 95% by mass of a block-copolymerized polypropylene resin, each percentage being relative to the whole polyolefin resin.
Description
Technical field
The present invention relates to be suitable as electric wire etc. coating flame retardant resin composition without halogen and use electric wire or the cable of this resin combination.
Background technology
In the internal wiring of OA equipment (as duplicating machine and printer) and electronic installation, used many wire harness, these wire harness are transmitting electric power and transmission signal between printed circuit board (PCB) and between printed circuit board (PCB) and electronic component are as sensor, performer and motor.
Article one, wire harness comprises the many electric wires that band together or cable and is assembled to electric wire or the terminal of cable end piece part (as insertable junctor).Consider flame retardant resistance, electrical insulating property etc., be used as the PVC electric wire of insulating material the electric wire that wire harness is used by comprising polyvinyl chloride (PVC).Because PVC electric wire has the flexible of excellence, even if therefore still obtained good manageability in the time being made into wire harness.In addition, because PVC electric wire has enough intensity, thereby during installation wiring, can there is not the problem such as isolator fracture or wearing and tearing.In addition, in the time that insulation displacement connector is assembled to the terminal portions of PVC electric wire, PVC electric wire has excellent fitting work.
But, because PVC electric wire contains halogen element, therefore in the time that wire harness used is carried out to burning disposal, may produce hydrogenchloride base toxic gas, or depend on and burning condition may produce dioxin, this is a problem.Therefore,, reducing under the requirement of carrying capacity of environment, do not think that PVC is desirable as insulating material.
In recent years, in order to meet the demand of the reduction carrying capacity of environment day by day increasing, developed such halogen electric wire: it uses the coating material that does not contain polyvinyl chloride (PVC) RESINS or halogen-based flame retardants.Meanwhile, conventionally require the electric wire used for electronic installation internal wiring to there is the multiple performance that meets UL (Underwriters Laboratories Ins. (American insurance business laboratory company)) standard as insulated line and insulated cable.UL standard has specified the multinomial performance that requires product satisfied, as the tensile property after incipient extension performance and the thermal ageing of flame retardant resistance, heating deformability, low-temperature performance and coating material.
With regard to the electric wire for insulation displacement contact or crimping, need to be at electronic installation internal layout wire harness.In this process, the possibility that has the insulation-coated possible impaired of electric wire or break, and therefore, electric wire may become defectiveness.Therefore, require to there is the high logical intensity (cut-through strength) of cutting for the insulated line of wire harness.
The open No.2002-105255 (patent documentation 1) of Japanese unexamined patent discloses a kind of fire-proof resin composition, it comprises thermoplastic resin composition and heats together with described thermoplastic resin composition and mixing metal hydrate, and described thermoplastic resin composition is by preparing elastomerics (as ethylene-propylene rubber or styrene butadiene rubbers) and acrylic resin blend.Can be by coordinating elastomerics carry out reinforcing filler acceptability, thus and think by this elastomerics has been carried out to the dynamic vulcanization balance mechanical property such as such as flexible and extensibility, extrude processibility and flame retardant resistance.But compared with PVC, the wear resistance of this material is low and resistance to steel edge intensity (cutting general character energy) is low.In the time attempting to improve these performances, flexible reduction, thus cause the balance between all performances to lose, this is a problem.
In addition, the open No.2008-169234 (patent documentation 2) of Japanese unexamined patent discloses a kind of flame retardant resin composition without halogen, and said composition has comprised the resinous principle and the nitrogen based flameproofing that contain polyamide resin or vibrin, polyphenyl ether resin and styrene-based elastomer resin.There is the hard polyphenyl ether resin and the soft styrene-based elastomer with high extensibility of high elastic coefficient by mixing, even and by further with still can maintain enough Young's modulus as crystalline resins and at the temperature that is equal to or higher than glass transition temp and keep the polyamide resin of extensibility or vibrin to mix, can obtain such insulated line, it has flexible, the wear resistance that is equal to PVC and the intensity of resistance to steel edge.
Reference listing
Patent documentation
Patent documentation 1: the open No.2002-105255 of Japanese unexamined patent
Patent documentation 2: the open No.2008-169234 of Japanese unexamined patent
Summary of the invention
Technical problem
Require to there is Gao Qietong intensity for the insulated line of wire harness, and compared with existing insulated line, need to improve intensity.Meanwhile, insulated line need to meet the requirement to flame retardant resistance, thermotolerance and mechanical property of defined in UL standard.Cut logical intensity in order to increase, what can conceive is that a large amount of mechanically resistant materials (, having the material of high elastic coefficient) are engaged in insulating material.In doing like this, there is tensile elongation, especially the tensile elongation after thermal ageing may reduce and thereby can not meet the possibility of UL standard.In addition, consider junctor assembling ability, strain relief (strain relief) may be destroyed.
Therefore, the object of this invention is to provide a kind of flame retardant resin composition without halogen, it has excellent in the physical strengths such as flexible and wear resistance, excellent flame retardant resistance, the excellent especially tensile function of cutting general character energy and meeting UL standard, and provides and use electric wire or the cable of this fire-proof resin composition as coating.
The solution of problem
The present invention relates to flame retardant resin composition without halogen, the phosphine flame retardant of the resinous principle that it comprises 100 mass parts and 5 to 40 mass parts, polyolefin resin, the polyphenyl ether resin of 10 to 50 mass parts and the styrene-based elastomer of 5 to 30 mass parts that the resinous principle of wherein said 100 mass parts comprises 30 to 85 mass parts; And described polyolefin resin comprise account for whole described polyolefin resins 5 quality % to 60 quality % pass through use the ethylene-propylene random copolymer that obtains of metallocene catalyst polymerisation, and account for the polypropylene block copolymer resin (claim 1) of 30 quality % to 95 quality % of whole described polyolefin resins.
Described polyphenyl ether resin is the mechanically resistant material at normal temperatures with high elastic coefficient.Described polyolefin resin has the flexible of excellence and can improve mechanical property.Described styrene-based elastomer not only has the flexible of excellence and extrudes processibility, but also serves as compatilizer.By adding compatilizer, polyolefin resin and polyphenyl ether resin mix each other satisfactorily, thereby can improve mechanical property.
As polyolefin resin, use ethylene-propylene random copolymer (hereinafter can be called " the random PP of metallocene ") and polypropylene block copolymer by adopting metallocene catalyst polymerisation to obtain.The random PP of metallocene has molecular weight and the degree of crystallinity of homogeneous, and comprises a small amount of low molecular weight compositions and low crystallised component.Therefore, the random PP of metallocene is flexible and has excellent heat-resistant aging, thereby is effective to improve the tensile elongation after tensile elongation and thermal ageing.On the other hand, polypropylene block copolymer has high elastic coefficient and is effective to increase and cuts logical intensity.By using the random PP of metallocene and polypropylene block copolymer as polyolefin resin using specific ratios, can obtain the tensile elongation of cutting after logical intensity and thermal ageing.As polyolefin resin, except described two types, can also use homo-polypropylene or polyethylene.
Relate to flame retardant resin composition without halogen according to claim 1 according to the invention of claim 2, wherein said polyolefin resin also comprises the Low Density Polyethylene of 5 quality % to the 20 quality % that account for whole polyolefin resins.By further mixing Low Density Polyethylene, can further improve the tensile elongation after tensile elongation and thermal ageing.
Relate to flame retardant resin composition without halogen according to claim 1 and 2 according to the invention of claim 3, it is characterized in that described styrene-based elastomer is the elastomer block copolymer of vinylbenzene and rubber constituent.Because this styrene-based elastomer is the elastomer block copolymer of vinylbenzene and rubber constituent, therefore improve the consistency between polyolefin resin and polyphenyl ether resin, and can obtain the resin combination with very good mechanical properties.
Relate to according to the flame retardant resin composition without halogen described in any one in claims 1 to 3 according to the invention of claim 4, it is characterized in that described polyphenylene oxide is the polyphenylene oxide resin that melt blending has polystyrene.By using melt blending to have the polyphenylene oxide resin of polystyrene, improve the workability during melting mixing and extruded processibility.
Relate to a kind of electric wire or cable according to the invention of claim 5, it uses described flame retardant resin composition without halogen as coating.The present invention can obtain there is excellent flame retardant resistance, flexible and cut the general character can halogen insulated line.
Relate to described electric wire or cable according to the invention of claim 6, it is characterized in that the thickness of coating is less than or equal to 0.3mm.Be to be less than or equal to 0.3mm at the thickness of insulating coating, as cut the general character can etc. characteristic with compared with the electric wire of routine techniques, there is significant difference, and realized excellent beneficial effect.
Relate to according to the electric wire described in claim 5 or 6 or cable according to the invention of claim 7, it is characterized in that described coating is by irradiating and be crosslinked with ionizing rays.Because coating is crosslinked, thermotolerance and physical strength are therefore improved.
Beneficial effect of the present invention
According to the present invention, a kind of flame retardant resin composition without halogen can be provided, it has excellent flame retardant resistance, excellent physical strength (as flexible and wear resistance), the excellent especially tensile function of cutting general character energy and meeting UL standard, and the electric wire or the cable that use this fire-proof resin composition are provided.
Brief Description Of Drawings
Fig. 1 illustrates the schematic diagram of measuring the method for cutting logical intensity.
Embodiments of the present invention
First, will the various materials for flame retardant resin composition without halogen be described.Polyphenylene oxide is a kind of engineering plastics that obtain by oxypolymerization 2，6-xylenol, and wherein said 2，6-xylenol is to use methyl alcohol and phenol as raw material and synthetic.In addition, the commercially available various materials that polystyrene and polyphenylene oxide melt blending are obtained to improve polyphenylene oxide forming process of passing through that have as modified polyphenylene ether resin.As the polyphenyl ether resin using in the present invention, can use polyphenylene oxide resin monomer and melt blending to have the polyphenylene oxide resin of polystyrene.In addition, can be before using suitably blend wherein introduced the polyphenylene oxide of carboxylic acid (as maleic anhydride).
When the polyphenylene oxide resin that uses melt blending to have a polystyrene is during as described polyphenyl ether resin, improved with styrene-based elastomer melting mixing during workability, this is preferred.Melt blending has the polyphenylene oxide resin of polystyrene and the consistency excellence of styrene-based elastomer.Therefore, the resin pressure during extruding reduces, and extrudes processibility and improve.
In this polyphenyl ether resin, heat-drawn wire changes according to the blending ratio of polystyrene.In the time that to use heat-drawn wire be 130 DEG C or higher polyphenyl ether resin, the physical strength of electric wire tunicle is high, and demonstrates excellent thermal deformation behavior, and this is preferred.Note, heat-drawn wire is defined as according to ISO75-1,2 method measured value under the load of 1.80MPa.
As the styrene-based elastomer using in the present invention, for example, can use styrene-ethylene butylene-styrene multipolymer, styrene-ethylene propylene-styrene multipolymer, styrene-ethylene-ethylene, propylene-styrol copolymer, vinylbenzene-butylene-styrene multipolymer etc., and the example comprises its hydropolymer and partially hydrogenated polymkeric substance thereof.In addition, can before using, suitably mix the styrene-based elastomer of wherein having introduced carboxylic acid (as maleic anhydride).
Especially, in the time using the elastomer block copolymer of vinylbenzene and rubber constituent, except extruding processibility raising, also improved fracture tensile elongation, and also improved shock-resistance, this is preferred.In addition, as segmented copolymer, can use triblock copolymer, as vinylbenzene-butylene-styrene segmented copolymer or the vinylbenzene-isobutylene-styrene copolymer of hydrogenation; Or diblock copolymer, as styrene-ethylene copolymers or styrene-ethylene propylene copolymer.In the time that styrene-based elastomer comprises 50 % by weight or more three block composition, improve electric wire by film strength and hardness, this is preferred.
In addition, consider mechanical property and flame retardant resistance, can suitably use styrene content 20 % by weight or more styrene-based elastomer.In the time that styrene content is less than 20 % by weight, hardness and extrude processibility decline.On the other hand, in the time that styrene content exceedes 50 % by weight, tensile fracture elongation rate declines, and this is not preferred.
In addition, as the melt flow rate (MFR) of molecular weight index (be abbreviated as " MFR ", according to JIS K 7210, measure under 230 DEG C × 2.16kgf) preferably in the scope of 0.8g/10 minute to 15g/10 minute.Its reason is, in the time that melt flow rate (MFR) is less than 0.8g/10 minute, extrudes processibility and decline, and in the time that melt flow rate (MFR) is greater than 15g/10 minute, physical strength declines.
The example of operable polyolefin resin comprises polypropylene (homopolymer, block polymer and unregulated polymer), polypropylene-base thermoplastic elastomer, response type (reactor-type) polypropylene-base thermoplastic elastomer, dynamic crosslinking type polypropylene-base thermoplastic elastomer, polyethylene (high density polyethylene(HDPE), linear low density polyethylene, Low Density Polyethylene, very low density polyethylene), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene-acrylic rubber, ethylene-methyl methacrylate glycidyl ester copolymer, the molecule of ethylene-methacrylic acid copolymer and wherein ethylene-methacrylic acid copolymer or ethylene-acrylic acid copolymer is by sodium, the metal ions such as zinc are by intermolecular bonding ionomer resin connected to one another.In addition, also can use by these resins of the modifications such as maleic anhydride, and these resins that contain epoxy group(ing), amino or imide.
In the middle of above-described polyolefin resin, the random PP of metallocene and polypropylene block copolymer are essential compositions.The content of the random PP of metallocene accounts for 5 quality % to 60 quality % of whole polyolefin resins, and the content of polypropylene block copolymer accounts for 30 quality % to 95 quality % of whole polyolefin resins.When the content of the random PP of metallocene is during lower than above-mentioned scope, the elongation after thermal ageing declines and can not meet UL standard.When the content of polypropylene block copolymer is during lower than above-mentioned scope, cut logical intensity and become not enough.In addition, in the time further containing the Low Density Polyethylene of 5 quality % to 20 quality % that accounts for whole polyolefin resins, can improve the elongation after elongation and thermal ageing, this is preferred.
As phosphine flame retardant, the polyphosphonitrile compound that can use phosphoric acid ester, metal phosphinate, melamine phosphate compound, ammonium phosphate compound, obtains by the ring-opening polymerization of ring phosphonitrile etc.These phosphine flame retardants can use separately, maybe can be used in combination wherein two or more.
The example of operable phosphoric acid ester comprises trimethyl phosphite 99, triethyl phosphate, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid cresols phenyl ester (cresyl phenyl phosphate), phosphoric acid cresols 2,6-diformazan phenyl ester, 2-ethylhexyl diphenyl phosphate, 1,3-phenylene two (diphenyl phosphoester), 1,3-phenylene two (two (2,6-3,5-dimethylphenyl) phosphoric acid ester), bisphenol-A two (diphenyl phosphoester), two (phenylbenzene) phosphoric acid ester of Resorcinol, octyl diphenyl phosphate, di(2-ethylhexyl)phosphate ethene ethyl ester, di(2-ethylhexyl)phosphate hydroxyl propylene butyl ester, ethene organic phosphate disodium salt (ethylene disodium ester phosphate), phosphoric acid tert-butyl benzene diphenyl ester (tert-butylphenyl diphenyl phosphate), two (tert.-butylbenzene) phenyl esters (bis-(tert-butylphenyl) phenyl phosphate) of phosphoric acid, tricresyl phosphate (trimethylphenylmethane) ester, p isopropylbenzoic acid benzene diphenyl ester (isopropylphenyl diphenyl phosphate), two (cumyl) diphenyl esters (bis-(isopropylphenyl) diphenyl phosphate) of phosphoric acid, tricresyl phosphate (isopropyl benzene) ester, tricresyl phosphate (2-ethyl hexyl) ester, tricresyl phosphate (butoxy second) ester, three iso-butyl ester of phosphoric acid, methyl-phosphorous acid, dimethyl methyl phosphonate, methyl-phosphorous acid diethyl ester, ethylphosphonic acid, propyl phosphonous acid, butyl phosphonic acids, 2-methyl-propyl phosphonous acid, tertiary butyl phosphonic acids, 2,3-dimethylbutyl phosphonic acids, octyl phosphonic acid, phenyl-phosphonic acid, diethyl phospho acid, methylethyl phospho acid, methyl-propyl phospho acid, dioctylphosphinic acid(HDOP), phenyl phosphinic acid, diethyl phenyl phospho acid, diphenyl phosphonic acid and alkyl phosphate.
Metal phosphinate is the compound by following formula (I) representative.In the formula, R
1and R
2representative has the alkyl of 1 to 6 carbon atom or has 12 or the aryl of carbon atom still less separately, and M represents calcium, aluminium or zinc, m=3 in the time that M is aluminium, situation m=2 in addition.
[Chemical formula 1]
The example of operable metal phosphinate comprises organic phospho acid aluminium salt, as EXOLIT OP1230, the EXOLIT OP1240, EXOLIT OP930 and the EXOLIT OP935 that are manufactured by Clariant K.K. Co., Ltd., and the blend of organic phospho acid aluminium salt (as EXOLIT OP1312) and polyphosphoric acid melamine.
The example of melamine phosphate compound comprises polyphosphoric acid melamine (as the MELAPUR200 being manufactured by Ciba Specialty Chemicals Co., Ltd.), polyphosphoric acid melamine acid, melamine phosphate, ortho-phosphoric acid trimeric cyanamide and melamine pyrophosphate.
The example of operable ammonium phosphate compound comprises ammonium polyphosphate, polyphosphoric acid acid amides, polyphosphoric acid acid amides ammonium salt and carboxylamine poly phosphate.
As the polyphosphonitrile compound obtaining by the ring-opening polymerization of ring phosphonitrile, can use SPR-100, the SA-100, SR-100, SRS-100 or the SPB-100L that are manufactured by Otsuka Chemicals Co., Ltd..
The content of phosphine flame retardant is 5 to 40 mass parts with respect to the resinous principle of 100 mass parts.In the time that this content is less than 5 mass parts, flame retardant resistance deficiency.In the time that this content exceedes 40 mass parts, mechanical property declines.The content of phosphine flame retardant is more preferably 5 quality to 30 mass parts.Before use, trimeric cyanamide, melamine cyanurate, lipid acid or silane coupling agent processing can be used in the surface of phosphine flame retardant.Substitute as carrying out in advance surface-treated, can carry out adding while wherein mixing with thermoplastic resin the overall blend of surface treatment agent.In addition, can use nitrogen based flameproofing together with phosphine flame retardant.As nitrogen based flameproofing, can use trimeric cyanamide, melamine cyanurate etc.
In addition, crosslinking coagent can be added in flame retardant resin composition without halogen of the present invention.As crosslinking coagent, can preferably use the polyfunctional monomer in molecule with multiple carbon-to-carbon double bonds, as trimethylolpropane trimethacrylate, triallyl cyanurate or triallyl isocyanurate.In addition, this crosslinking coagent liquid preferably at normal temperatures.Its reason is, easily mixes with polyphenyl ether resin and styrene-based elastomer as liquid.In addition, in the time using trimethylolpropane trimethacrylate as crosslinking coagent, the consistency of raising and resin, this is preferred.
As required, antioxidant, processing stabilizers, tinting material, heavy metal deactivator, whipping agent, polyfunctional monomer etc. suitably can be sneaked in flame retardant resin composition without halogen of the present invention.These materials can use known melt mixer to mix as short screw extrusion type mixing tank, pressure kneader or Banbury mixer.
Insulated line of the present invention has the coating that fire-proof resin composition forms by mentioned earlier, and wherein said coating directly forms on conductor, or between exists in the situation of another layer and forms.Can use known forcing machine (as melt extruder) insulation-coated layer as described in forming.In addition, this insulation layer is preferably by irradiating and be crosslinked with ionizing rays.
As conductor, can use copper cash, the aluminum steel etc. with excellent electric conductivity.Although can suitably select according to desired use the diameter of conductor, for wiring is installed in narrow space, this diameter is to be preferably made as 2mm or less.In addition, consider easy handling, this diameter is preferably located at 0.1mm or less.Conductor can be solid conductor or many wire strandings stranded conductor together.
Although can suitably select according to the diameter of conductor the thickness of coating, consider physical strength, thickness is preferably made as 0.3mm or less.In the halogen electric wire obtaining according to routine techniques, when the thickness of coating is 0.3mm or more hour, wear resistance and Qie Tong strength degradation.On the contrary, in the present invention, even when the thickness of coating be 0.3mm or more hour, still obtain excellent performance, and have significant difference with the electric wire according to routine techniques.In addition, in the electric wire of insulation displacement contact use, consider junctor assembling ability, preferably using the wherein thickness of coating is 0.3mm or less electric wire.
In the time that this coating is crosslinked by irradiating with ionizing rays, improve physical strength, this is preferred.As ionized radiation source, for example, can use electron beam, gamma rays, X ray, alpha ray, ultraviolet ray of acceleration etc.Consider and use the easy degree of source of radiation, ionizing rays to transmit thickness, crosslinking Treatment speed etc., from the viewpoint of industrial application, can most preferably use accelerated electron beam.
Embodiment
Below will based on following examples, the present invention will be described in more detail.But, be to be understood that and the invention is not restricted to described embodiment.
[embodiment 1 to 5]
(formation of flame retardant resin composition without halogen pellet)
Mix each composition according to the formula shown in Table I.In this table, the linear module of matrix resin, fire retardant, degradation inhibitor and crosslinking coagent is mass parts.Use double-screw mixer (45mm Φ, L/D=42), under the bolt rotary speed of the cylinder temperature of 240 DEG C and 100 revs/min, carry out melting mixing, and mixture is melt extruded into twisted wire.Subsequently, by cooling melting twisted wire and cutting with form pellet.
(making of insulated line)
Use single screw extrusion machine (30mm Φ, L/D=24), at conductor (7 stranded tinannealed copper wires; Conductor diameter: 0.42mm) on extrude coating, making thickness is 0.14mm.With the acceleration voltage of 2MeV irradiate 30 or the electron beam of the amount of 60kGy to make insulated line.It should be noted in the discussion above that sample that use only comprises the coating that takes out conductor and obtain from insulated line evaluates mechanical property (initial and thermal ageing after).
(evaluation of coating: tensile property)
From the electric wire of made, take out conductor, and coating is carried out to tension test.Test condition is as follows: draw rate=500mm/ minute, distance between bench marks is from=25mm, and temperature=23 DEG C.Respectively to 3 sample measurement tensile strengths and tensile elongation (elongation at break), and determine its mean value.By have 10.3MPa or larger tensile strength and 150% or the sample of larger tensile elongation be evaluated as " passing through ".
(evaluation of coating: secant modulus)
Use and tension test mentioned above in similar sample, carry out under the following conditions tension test: draw rate=500mm/ minute, distance between bench marks is from=25mm, and temperature=23 DEG C.Subsequently, the Young's modulus while being 2% from stress-extension curve calculating elongation.
(evaluation of coating: thermotolerance)
It is in the Geer baking oven of 136 DEG C 168 hours (7 days) that insulated line is statically placed in to temperature.Subsequently, as evaluated in tensile property, carry out tension test, and with thermal treatment before tensile strength and tensile elongation comparison.By the residual rate of tensile strength before thermal treatment be more than or equal to 75% and thermal treatment before the residual rate of tensile elongation be defined as qualified level for being more than or equal to 45%.
(evaluation of insulated line: flame retardant test)
The content of recording according to UL standard 1581 the 1080th chapter is carried out VW-1 sample testing vertical flammability to 5 parts of samples.When flame is applied to every part of sample 15 seconds and repeats 5 times, it is qualified evaluating following situation: burning stopped in 60 seconds, and the material that the absorbent cotton below being positioned at is not dripped is lighted, and the kraft paper being connected with sample upside is not burning or burning.Even if having a sample not reach qualified level in 5 parts of samples, be unsuccessfully by this average evaluation.
(evaluation of insulated line: cut logical intensity)
Use the measuring apparatus shown in Fig. 1, measure and cut logical intensity.The blade 4 that makes to have 90 ° of sharp edges (edge R=0.125mm, 90 ° of edge angles) contacts with the insulated line 3 that comprises conductor 1 and coating 2, and measures the value that flows through the electric current between conductor and sharp edge.In original state, because conductor and sharp edge are isolated each other by coating 2, therefore electric current does not flow through.In the time that coating 2 is cut off by blade 4, electric current flows through between conductor and sharp edge.Load is applied to blade 4, and measurement coating 2 be not cut off the overall loading of bearing in situation.Under the environment of 23 DEG C of temperature and 50%RH humidity, carry out this test.Be qualified level by 70N or larger load definition.
[comparative example 1 to 7]
As in embodiment 1 to 5, make insulated line, difference is, uses and has the resin combination of filling a prescription shown in Table II, and carry out a series of evaluations.In this table, the linear module of matrix resin, fire retardant, degradation inhibitor and crosslinking coagent is mass parts.The results are shown in Table II.
(footnote)
(
*1) polypropylene block copolymer resin: the Novatec EC9 being manufactured by Japan Polypropylene Co., Ltd.
(
*2) ethylene-propylene random copolymer of use metallocene catalyst polymerisation: the WELNEX RFG4VA being manufactured by Japan Polypropylene Co., Ltd.
(
*3) homo-polypropylene: the Novatec EA9BT being manufactured by Japan Polypropylene Co., Ltd.
(
*4) Low Density Polyethylene: the NUC-8007 (MFR=7g/10 minute) being manufactured by Nippon Unicar Co., Ltd..
(
*5) polyphenylene oxide resin that intrinsic viscosity is 0.47dl/g
(
*6) styrene-based elastomer: manufactured by Asahi Kasei Co., Ltd.: Tuftec (registered trademark) H1043
(
*7) condensed phosphoric acid esters: the PX-200 (phosphorus 9.0%) being manufactured by Daihachi Chemical Industry Co., Ltd.
(
*8) Irganox1010 being manufactured by Chiba Specialty Co., Ltd.
(
*9) manufacture SEENOX 412S by Shipro Kasei Kaisha Co., Ltd.
(
*10) trimethylolpropane trimethacrylate: the TD1500S being manufactured by Dainippon Ink Chemicals
The insulated line of embodiment 1 to 5 all has 70N or larger cuts logical intensity, thereby has high strength.In addition, the tensile elongation after incipient extension elongation and thermal ageing reaches qualified level.Compared with wherein not using the embodiment 1 of Low Density Polyethylene, wherein use the tensile elongation after the thermal ageing in the embodiment 2 to 5 of Low Density Polyethylene high.In addition, in the time that the content of the random PP of metallocene increases, the tensile elongation after tensile elongation and thermal ageing increases.
In the insulated line of comparative example 1 to 7, flame retardant resin composition without halogen used does not contain the random PP of metallocene.In whole these insulated lines, although it is high and in qualified level to cut logical intensity, therefore tensile elongation after thermal ageing is low is evaluated as failure.In comparative example 6 and 7, add the homopolymerization PP with high elastic coefficient, therefore described resin combination has high elastic coefficient.Although cut the Young's modulus height of logical intensity because improving, the tensile elongation after thermal ageing is low, therefore it does not reach qualified level.
Description of reference numerals
1 conductor
2 coatings
3 insulated lines
4 blades
Claims (7)
1. a flame retardant resin composition without halogen, the phosphine flame retardant of the resinous principle that comprises 100 mass parts and 5 to 40 mass parts,
Polyolefin resin, the polyphenyl ether resin of 10 to 50 mass parts and the styrene-based elastomer of 5 to 30 mass parts that the resinous principle of wherein said 100 mass parts comprises 30 to 85 mass parts; And
Described polyolefin resin comprise account for whole described polyolefin resins 5 quality % to 60 quality % pass through to use the ethylene-propylene random copolymer that obtains of metallocene catalyst polymerisation and the polypropylene block copolymer resin that accounts for 30 quality % to 95 quality % of whole described polyolefin resins.
2. flame retardant resin composition without halogen according to claim 1, wherein said polyolefin resin also comprises the Low Density Polyethylene of 5 quality % to the 20 quality % that account for whole described polyolefin resins, and the total mass per-cent of each moiety in described polyolefin resin is 100 quality %.
3. flame retardant resin composition without halogen according to claim 1, wherein said styrene-based elastomer is the elastomer block copolymer of vinylbenzene and rubber constituent.
4. flame retardant resin composition without halogen according to claim 1, wherein said polyphenylene oxide is the polyphenylene oxide resin that melt blending has polystyrene.
5. electric wire or a cable, it uses according to the flame retardant resin composition without halogen described in any one in claim 1 to 4 as coating.
6. electric wire according to claim 5 or cable, the thickness of wherein said coating is less than or equal to 0.3mm.
7. electric wire according to claim 5 or cable, wherein said coating is by irradiating and be crosslinked with ionizing rays.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-094526 | 2010-04-16 | ||
| JP2010094526 | 2010-04-16 | ||
| PCT/JP2011/051382 WO2011129129A1 (en) | 2010-04-16 | 2011-01-26 | Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102858873A CN102858873A (en) | 2013-01-02 |
| CN102858873B true CN102858873B (en) | 2014-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201180003851.6A Expired - Fee Related CN102858873B (en) | 2010-04-16 | 2011-01-26 | Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP5549675B2 (en) |
| KR (1) | KR20130057961A (en) |
| CN (1) | CN102858873B (en) |
| MY (1) | MY167034A (en) |
| SG (1) | SG183785A1 (en) |
| TW (1) | TW201247854A (en) |
| WO (1) | WO2011129129A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5843644B2 (en) * | 2011-09-28 | 2016-01-13 | 三井化学株式会社 | Thermoplastic polymer composition, molded article comprising the same, and electric wire |
| JP5494688B2 (en) * | 2012-02-03 | 2014-05-21 | 住友電気工業株式会社 | Halogen-free flame retardant insulated wire |
| CN103804835A (en) * | 2012-11-06 | 2014-05-21 | 广东聚石化学股份有限公司 | Halogen-free flame retardant thermoplastic elastomer cable material and preparation method thereof |
| CN103194014B (en) * | 2013-04-08 | 2015-04-01 | 刘平 | Halogen-free flame-retardant polyolefin material |
| CN103360752B (en) * | 2013-07-15 | 2015-10-28 | 上海秋橙新材料科技有限公司 | anti-aging PPO-ABS plastic alloy |
| JP5808023B2 (en) * | 2013-11-15 | 2015-11-10 | 株式会社ジェイ・パワーシステムズ | Flame retardant ant cable |
| KR101720407B1 (en) * | 2014-02-28 | 2017-04-04 | 주식회사 엘지화학 | Fire retardant thermoplastic resin composition and electric wire comprising the same |
| KR101960350B1 (en) | 2015-06-17 | 2019-03-20 | 주식회사 엘지화학 | Polypropylene resin composition and a cable covered therefrom |
| KR101745107B1 (en) | 2015-07-09 | 2017-06-08 | 현대자동차주식회사 | Resin composition for automotive wire material and electric wire using it |
| US20180127580A1 (en) | 2015-07-22 | 2018-05-10 | Asahi Kasei Kabushiki Kaisha | Resin composition and shaped product |
| JP6418138B2 (en) * | 2015-11-25 | 2018-11-07 | 住友電気工業株式会社 | Flame retardant resin composition and flame retardant cable |
| JP6418137B2 (en) * | 2015-11-25 | 2018-11-07 | 住友電気工業株式会社 | Flame retardant resin composition and flame retardant cable |
| KR101932254B1 (en) * | 2016-06-14 | 2018-12-26 | (주) 솔루켐 | Insulated wire with non-halogenated insulated covered wire compositon |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679720A (en) * | 2008-04-09 | 2010-03-24 | 住友电气工业株式会社 | Frpipe and use the heat-shrinkable tube of this Frpipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000026696A (en) * | 1998-07-14 | 2000-01-25 | Sumitomo Wiring Syst Ltd | Flame retardant and abrasion resistant resin composition |
| JP4002061B2 (en) * | 2000-10-03 | 2007-10-31 | 古河電気工業株式会社 | Flame retardant resin composition for covering electric wire or optical fiber and wiring material using the same |
| JP5546096B2 (en) * | 2007-03-22 | 2014-07-09 | 旭化成ケミカルズ株式会社 | Thermoplastic polymer rubber composition |
-
2011
- 2011-01-26 MY MYPI2012700074A patent/MY167034A/en unknown
- 2011-01-26 KR KR1020127006800A patent/KR20130057961A/en not_active Application Discontinuation
- 2011-01-26 WO PCT/JP2011/051382 patent/WO2011129129A1/en active Application Filing
- 2011-01-26 SG SG2012015020A patent/SG183785A1/en unknown
- 2011-01-26 CN CN201180003851.6A patent/CN102858873B/en not_active Expired - Fee Related
- 2011-01-26 JP JP2011536221A patent/JP5549675B2/en not_active Expired - Fee Related
- 2011-02-10 TW TW100104367A patent/TW201247854A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679720A (en) * | 2008-04-09 | 2010-03-24 | 住友电气工业株式会社 | Frpipe and use the heat-shrinkable tube of this Frpipe |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5549675B2 (en) | 2014-07-16 |
| MY167034A (en) | 2018-08-02 |
| KR20130057961A (en) | 2013-06-03 |
| CN102858873A (en) | 2013-01-02 |
| WO2011129129A1 (en) | 2011-10-20 |
| JPWO2011129129A1 (en) | 2013-07-11 |
| SG183785A1 (en) | 2012-11-29 |
| TW201247854A (en) | 2012-12-01 |
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