CN101359520B - Non-halgen flame retardant wire - Google Patents
Non-halgen flame retardant wire Download PDFInfo
- Publication number
- CN101359520B CN101359520B CN2008101112174A CN200810111217A CN101359520B CN 101359520 B CN101359520 B CN 101359520B CN 2008101112174 A CN2008101112174 A CN 2008101112174A CN 200810111217 A CN200810111217 A CN 200810111217A CN 101359520 B CN101359520 B CN 101359520B
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- China
- Prior art keywords
- weight portions
- flame retardant
- internal layer
- halgen
- maleic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- 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
- H01B3/44—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
- H01B7/0208—Cables with several layers of insulating material
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Insulated Conductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a halogen free flame retardant electronic wire that has excellent characteristics of flexibility and voltage resistance by optimizing resin match in an electrical insulator formed by an inner and an outer layer. The halogen free flame retardant electronic wire insulates in periphery of a conductor (2) by an electrical insulator (5) formed by an inner and an outer layer (3, 4). The inner layer (3) is formed by adding improved ethylene/ethyl acrylate polymer by maleic anhydride of 5 weight parts to 40 weight parts and metal hydroxids (improving rate of the maleic anhydride is 1% to 40%) in 100 weight parts of ethylene/ethyl acrylate polymer with content of vinyl acetate is more than or equal to 60% but less than or equal to 80%. The outer layer (4) is formed by adding metal hydroxids in the ethylene/ethyl acrylate polymer with content of vinyl acetate is more than or equal to 30% but less than or equal to 60%. In addition, thickness of the formed outer layer (4) is greater than that of the inner layer (3).
Description
Technical field
The present invention relates to a kind of non-halgen flame retardant wire, its halogen insualtion resin composition by inside distribution that is used for electric equipment etc. forms, and has flexibility and proof voltage.
Background technology
In recent years, in order to solve environmental problem, and developed the halogen free flame retardant resin composition that when burning, does not produce harmful halogen gass such as dioxin, as the insulating coating material of electric wire or cable etc.As flame retardant resin composition without halogen, known have in ethylene-vinyl acetate copolymer (EVA) or maleic anhydride modified ethylene-ethyl acrylate copolymer copolymers such as (maleic anhydride modified EEA), mixing is as the metal hydroxides of fire retardant and the composition (for example, with reference to patent documentation 1) that forms.
On the other hand, if increase the combined amount of fire retardant in order to improve anti-flammability, mechanical properties and electrical characteristic are descended.As its countermeasure, known have by internal layer and outer these 2 layers of insulating barriers that forms electric wire.But; if in order to make skin further have anti-flammability; in the polyolefin of 100 weight portions, add the magnesium hydroxide of 300 weight portions; and make the electrical insulator layer thickening in order to ensure mechanical property and electrical characteristic; then when being exposed to electric wire on the flame; polyolefin the time can flow in burning, gasifies subsequently and burns.
To this, for example in patent documentation 2 disclosed technology, the electric wire of following structure is disclosed.
Internal layer be in the matrix resin of 100 weight portions, add the fire retardant of 50～150 weight portions and form the layer.Matrix resin is following 2 kinds.A kind of is that ethyl acrylate (EA) content is the ethylene-ethyl acrylate copolymer (EEA) of 9～35 weight %.Another kind of in EEA, being mixed with other polyolefin.Fire retardant is a magnesium hydroxide etc.
Skin be in the matrix resin of 100 weight portions, add the fire retardant of 150～300 weight portions and form the layer.Matrix resin is following 4 kinds.A kind of is the EEA of 15～35 weight % for EA content.Second kind is EEA and other polyolefinic mixtures.The third is that vinylacetate (VA) content is the ethylene-vinyl acetate copolymer (EVA) of 15～45 weight %.The 4th kind is EVA and other polyolefinic mixtures.Fire retardant is a magnesium hydroxide etc.
Patent documentation 1: TOHKEMY 2003-160709 communique
Patent documentation 2: TOHKEMY 2006-286529 communique
Summary of the invention
Invent problem to be solved
Though people need have the non-halgen flame retardant wire of flexibility and proof voltage,, the percentage elongation of electrical insulator is reduced if in as the EVA of matrix resin, add maleic anhydride modified EEA.That is, the flexibility of insulated electric conductor reduces and hardening.On the other hand,, can suppress the electrical insulator moisture absorption, and the proof voltage of insulated electric conductor is improved by in as the EVA of matrix resin, adding maleic anhydride modified EEA.
In addition, increase, then can make the insulated electric conductor softness if make as the VA content among the EVA of matrix resin.But, if the VA content among the EVA continues to uprise, then produce such problem: when the coiling insulated electric conductor, stick together between the electric wire, and tensile strength descends and fracture easily.
The present invention In view of the foregoing proposes, its purpose is to provide a kind of non-halgen flame retardant wire, it is by optimizing by the resin proportioning in internal layer and outer these 2 layers of electrical insulators that constitutes, thereby makes this non-halgen flame retardant wire have flexibility and all excellent characteristic of proof voltage.
The means of dealing with problems and being adopted
Non-halgen flame retardant wire involved in the present invention is by by internal layer and outer these 2 layers of non-halgen flame retardant wires that the electrical insulator that constitutes insulate in the periphery of electric conductor.It is characterized in that, internal layer is for being less than or equal in 80% ethylene-vinyl acetate copolymer 100 weight portions more than or equal to 60% in vinyl acetate content, add maleic anhydride modified ethylene-ethyl acrylate copolymer (maleic anhydride modified rate is 1～40%) 5 weight portions～40 weight portions and metal hydroxides and form, skin is to form for adding metal hydroxides more than or equal to 30% in less than 60% ethylene-vinyl acetate copolymer in vinyl acetate content.In addition, the outer field thickness that is preferably formed is than the thin thickness of internal layer.
The effect of invention
According to the present invention, by improving, can guarantee to have flexibility, and, can improve proof voltage by adding polyethylene maleic anhydride ethyl acrylate 3 membered copolymers as the vinyl acetate content in the ethylene-vinyl acetate copolymer of internal layer matrix resin.In addition, by reducing as the vinyl acetate content in the ethylene-vinyl acetate copolymer of outer matrix resin, can make the surface hardening of electrical insulator, and the inhibition electric wire bonds mutually, simultaneously the tensile strength of electric wire can be improved, thereby non-halgen flame retardant wire can be formed with flexibility and proof voltage.
Description of drawings
Fig. 1 is the figure that summary illustrates non-halgen flame retardant wire involved in the present invention.
The explanation of label
1 non-halgen flame retardant wire 2 electric conductors, 3 electrical insulators (internal layer) 4 electrical insulators (skin), 5 electrical insulators
Embodiment
As shown in Figure 1, non-halgen flame retardant wire 1 involved in the present invention is object with the outside at electric conductor 2 by electric wire or the cable that electrical insulator 5 is covered, wherein this electrical insulator 5 by internal layer 3 and outer 4 these 2 layers constitute.What in addition, electric conductor 2 used is that for example section is the zinc-plated single core annealed copper wire of circle or the annealed copper wire of 7 strands of twisteds.The internal layer 3 of electrical insulator 5 and outer 4 all uses the halogen-free flame-retardant resin, this halogen-free flame-retardant resin is a matrix resin with the ethylene-vinyl acetate copolymer (EVA) as polyolefin resin, is added with the metal hydroxides as fire retardant in this matrix resin.
Owing in molecule, have oxygen element as the EVA of matrix resin, thus its have self anti-flammability height and and metal hydroxides between the also high character of compatibility.In addition, EVA is the thermoplastic resin that ethene and vinylacetate (VA) copolymerization form, and along with the content of VA increases, its flexibility increases, and demonstrates the character approaching with rubber.The content of VA EVA more after a little while demonstrates the character approaching with low density polyethylene (LDPE), has higher tensile strength but toughness is stronger.Therefore, if use the more EVA of VA content to form electrical insulator 5 for the flexibility that obtains electric wire, then the electric wire surface becomes sticky, thereby the contact portion of electric wire is bondd easily mutually, is difficult to handle.
In the present invention, make that VA content increases among the EVA of internal layer 3 of electrical insulator 5, to obtain the required flexibility of the electric wire of distribution in equipment easily, make simultaneously that VA content reduces among outer 4 the EVA, so that the surface hardening of electrical insulator 5.Specifically, the VA content of internal layer 3 is less than or equal at 80% o'clock more than or equal to 60%, can make non-halgen flame retardant wire have flexibility, and outer 4 VA content less than 60% more than or equal to 30% o'clock, can make the non-halgen flame retardant wire sclerosis.Thus, the outer surface of electrical insulator 5 can not become sticky, also can guarantee to have tensile strength to a certain degree, thereby can make electric wire reel easily and be convenient to handle during distribution.
In addition, in the EVA of internal layer 3, add maleic anhydride modified ethylene-ethyl acrylate copolymer (EEA).Though this maleic anhydride modified EEA has improved thermal endurance, mechanical strength, percentage elongation descends.But maleic anhydride modified EEA has the electrical insulator of inhibition by the effect of water swelling, therefore, by adding this maleic anhydride modified EEA, can improve the voltage-resistent characteristic of electrical insulator.In addition, do not carry out maleic anhydride modified EEA and do not have the effect that suppresses swelling, and owing to there is not ions binding between the acidic-group, thus descend with the conjugation of EVA, thus can't obtain required fracture strength.
Specifically, the degree of modification of maleic anhydride modified EEA is 1～40%, in the EVA of 100 weight portions, adds the maleic anhydride modified EEA about 5～40 weight portions, preferably adds 15～35 weight portions.In addition, during addition less than 5 weight portions, can't expect to have moisture absorption basically and suppress effect, and if addition surpasses 40 weight portions, then crystallised component becomes many, so variation such as flexibility, bendabilities.
In order to ensure the flexibility of electric wire, preferably, the thickness of the skin 4 that flexibility is lower than internal layer 3 is than the thin thickness of internal layer 3.The gross thickness of electrical insulator 5 is different and different according to thickness of desired proof voltage and electric conductor etc., for example, if rated voltage is 6kV (AC), and the thickness of employed electric conductor is AWG20～30 (diameter 0.81mm～0.25mm), then preferably, the thickness of internal layer 3 is 0.4mm～0.5mm, and outer 4 thickness is 0.1mm～0.2mm, and internal layer and outer field aggregate thickness are 0.5mm～0.7mm.If the thickness of electrical insulator 5 is blocked up, then be difficult to bending, flexibility descends, and causes being difficult to handling, and needs distribution space in the bigger equipment, thereby make equipment enlarging.
In addition, the same with prior art, in the internal layer 3 and outer 4 of electrical insulator 5, add metal hydroxides respectively as fire retardant.Described metal hydroxides for example can use magnesium hydroxide, aluminium hydroxide, calcium hydroxide etc., but wherein the flame retardant effect of magnesium hydroxide is better, so preferred.In addition, in order to improve the compatibility between these metal hydroxidess and the matrix resin, also can use by titanate coupling agent, silane couplers such as vinyl silanes, epoxy radicals silicone hydride, amino silane, metering system base silane, senior aliphatic acid such as stearic acid, oleic acid, laurate carry out the metal hydroxides after the surface treatment.
In the matrix resin of the internal layer 3 of the electrical insulator of 100 weight portions and outer 4, add the fire retardant that constitutes by above-mentioned metal hydroxides of 50 weight portions～200 weight portions.Concrete addition depends on desired fire-retardant degree, if but addition less than 50 weight portions then the anti-flammability deficiency, if addition surpasses 200 weight portions, then the fracture strength of electrical insulator, percentage elongation descend.
In addition, in any one deck in the internal layer 3 and outer 4 of the above-mentioned electrical insulator 5 that forms by the halogen free flame retardant composition, can in the matrix resin of 100 weight portions, add the antioxidant of 0.1 weight portion～5.0 weight portions as required, the resin embrittlement that this antioxidant can suppress to be caused by thermal oxidation.In addition, can also add various auxiliary agents such as processing aid that the mouldability that makes electrical insulator 5 improves, colouring agent, stabilizer.
According to ULstandard 758 (Unite States Standard), the non-halgen flame retardant wire 1 among the present invention satisfy following shown in the result.
(1) anti-flammability meets UL VW-1.
(2) about flexibility (percentage elongation), behind the extraction electric conductor, the elongation at break of remaining electrical insulator (body) is more than or equal to 150% from electric wire.
(3) about tensile strength, the fracture strength of above-mentioned electrical insulator (body) is more than or equal to 10.3MPa.
(4) about proof voltage (is under the situation of AC 6kV in rated voltage), wiring harness is immersed in the water after 24 hours (expose the end), between the power and water line, apply the voltage 1 minute of 13kV, voltage breakdown does not take place.
(embodiment 1)
Electric conductor: tin annealed copper wire (AWG24, conductor structure are 7/0.203, and external diameter is 0.61mm)
Electrical insulator: VA content is 70% EVA 100 weight portions
(internal layer) maleic anhydride modified EEA (degree of modification 25%) 20 weight portions
Magnesium hydroxide 180 weight portions
Layer thickness 0.42mm
Electrical insulators: VA content is 50% EVA 100 weight portions
(skin) magnesium hydroxide 180 weight portions
Layer thickness 0.13mm
The electric wire of the foregoing description 1 reaches the flame-retardancy standards (UL VW-1) of regulation, and proof voltage reaches 13kV (1 minute) simultaneously, and percentage elongation is 170%, and tensile strength is 11.5MPa, so satisfy the value of regulation.
(embodiment 2: internal layer is identical with outer field thickness)
Electric conductor: tin annealed copper wire (AWG24, conductor structure are 7/0.203, and external diameter is 0.61mm)
Electrical insulator: VA content is 70% EVA 100 weight portions
(internal layer) maleic anhydride modified EEA (degree of modification 25%) 20 weight portions
Magnesium hydroxide 180 weight portions
Layer thickness 0.27mm
Electric insulation layer: VA content is 50% EVA 100 weight portions
(skin) magnesium hydroxide 180 weight portions
Layer thickness 0.27mm
The electric wire of the foregoing description 2 is the examples when making internal layer identical with outer field thickness in embodiment 1, it reaches the flame-retardancy standards (UL VW-1) of regulation, proof voltage reaches 13kV (1 minute) simultaneously, percentage elongation is 150%, tensile strength is 10.5MPa, satisfy the value of regulation, but compare with embodiment 1, percentage elongation and tensile strength are slightly poor.
(comparative example 1: do not add maleic anhydride modified EEA in the internal layer)
Electric conductor: tin annealed copper wire (AWG24, conductor structure are 7/0.203, and external diameter is 0.61mm)
Electrical insulator: VA content is 70% EVA 100 weight portions
(internal layer) magnesium hydroxide 180 weight portions
Layer thickness 0.42mm
Electric insulation layer: VA content is 50% EVA 100 weight portions
(skin) magnesium hydroxide 180 weight portions
Layer thickness 0.13mm
(comparative example 2: the EEA in the internal layer is not by maleic anhydride modified)
Electric conductor: tin annealed copper wire (AWG24, conductor structure are 7/0.203, and external diameter is 0.61mm)
Electrical insulator: VA content is 70% EVA 100 weight portions
(internal layer) EEA 20 weight portions
Magnesium hydroxide 180 weight portions
Layer thickness 0.42mm
Electric insulation layer: VA content is 50% EVA 100 weight portions
(skin) magnesium hydroxide 180 weight portions
Layer thickness 0.13mm
Comparative example 1 is the example when not adding maleic anhydride modified EEA (20 weight portion) in internal layer in embodiment 1, though flexibility, tensile strength reach setting, can't satisfy proof voltage.In addition, comparative example 2 is to add not the example when replacing maleic anhydride modified EEA by maleic anhydride modified simple EEA in embodiment 1 in internal layer, and is the same with comparative example 1, though flexibility, tensile strength reach setting, can't satisfy proof voltage.
According to above-mentioned result of the test, by improving, can guarantee that non-halgen flame retardant wire has flexibility, and, can improve proof voltage by adding maleic anhydride modified ethylene-ethyl acrylate copolymer as the VA content among the EVA of internal layer matrix resin.And, by reducing as the VA content among the EVA of outer matrix resin, thereby the surface hardening that can make non-halgen flame retardant wire can suppress electric wire to bond mutually, can improve simultaneously the percentage elongation and the tensile strength of electrical insulator, have the two non-halgen flame retardant wire of flexibility and proof voltage thereby form.
In addition, the outer field thickness by making electrical insulator can further improve above-mentioned action effect than the thin thickness of internal layer.
Claims (2)
1. non-halgen flame retardant wire, its in the periphery of electric conductor by by internal layer and outer these 2 layers of non-halgen flame retardant wires that the electrical insulator that is constituted insulate,
It is characterized in that, described internal layer is in vinyl acetate content is 60%～80% ethylene-vinyl acetate copolymer 100 weight portions, adding maleic anhydride modified rate and be 1～40% maleic anhydride modified ethylene-ethyl acrylate copolymer 5 weight portions～40 weight portions and metal hydroxides forms
Described skin is to form for adding metal hydroxides more than or equal to 30% in less than 60% ethylene-vinyl acetate copolymer in vinyl acetate content.
2. the described non-halgen flame retardant wire of claim 1 is characterized in that, formed described outer field thickness is than the thin thickness of described internal layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007149232A JP5194570B2 (en) | 2007-06-05 | 2007-06-05 | Halogen-free flame retardant wire |
| JP2007149232 | 2007-06-05 | ||
| JP2007-149232 | 2007-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101359520A CN101359520A (en) | 2009-02-04 |
| CN101359520B true CN101359520B (en) | 2011-10-12 |
Family
ID=40234126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101112174A Expired - Fee Related CN101359520B (en) | 2007-06-05 | 2008-06-05 | Non-halgen flame retardant wire |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5194570B2 (en) |
| KR (1) | KR20080107316A (en) |
| CN (1) | CN101359520B (en) |
| TW (1) | TW200908028A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5652452B2 (en) * | 2012-09-27 | 2015-01-14 | 日立金属株式会社 | Non-halogen flame retardant insulated wire |
| KR20140070028A (en) * | 2012-11-30 | 2014-06-10 | 엘에스전선 주식회사 | Retardant electronic cable with excellent flexibility |
| CN110164589B (en) * | 2015-09-30 | 2021-04-23 | 住友电气工业株式会社 | Core wire for multi-core cable and multi-core cable |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715321A (en) * | 2004-06-29 | 2006-01-04 | 信越化学工业株式会社 | Flame retardant resin composition without halogen |
| CN1828783A (en) * | 2005-03-04 | 2006-09-06 | 日立电线株式会社 | Non-halogen flame resistant wire and cable |
| CN1848306A (en) * | 2005-04-04 | 2006-10-18 | 日立电线株式会社 | Non-halogen fire-retardancy electric wire and cable |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04311742A (en) * | 1991-04-10 | 1992-11-04 | Mitsubishi Cable Ind Ltd | Insulating composition |
| JP2003132741A (en) * | 2001-10-29 | 2003-05-09 | Fujikura Ltd | Insulated electric wire |
| JP2005139388A (en) * | 2003-11-10 | 2005-06-02 | Hitachi Cable Ltd | Nonhalogen resin composition, and electric wire or cable by using the composition |
| JP4737362B2 (en) * | 2003-12-24 | 2011-07-27 | 東ソー株式会社 | Ethylene-vinyl acetate copolymer and flame retardant resin composition |
-
2007
- 2007-06-05 JP JP2007149232A patent/JP5194570B2/en not_active Expired - Fee Related
-
2008
- 2008-06-04 TW TW097120669A patent/TW200908028A/en unknown
- 2008-06-05 KR KR1020080053346A patent/KR20080107316A/en not_active Application Discontinuation
- 2008-06-05 CN CN2008101112174A patent/CN101359520B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715321A (en) * | 2004-06-29 | 2006-01-04 | 信越化学工业株式会社 | Flame retardant resin composition without halogen |
| CN1828783A (en) * | 2005-03-04 | 2006-09-06 | 日立电线株式会社 | Non-halogen flame resistant wire and cable |
| CN1848306A (en) * | 2005-04-04 | 2006-10-18 | 日立电线株式会社 | Non-halogen fire-retardancy electric wire and cable |
| JP2006286529A (en) * | 2005-04-04 | 2006-10-19 | Hitachi Cable Ltd | Halogen free flame retardant cable |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200908028A (en) | 2009-02-16 |
| JP5194570B2 (en) | 2013-05-08 |
| CN101359520A (en) | 2009-02-04 |
| JP2008305569A (en) | 2008-12-18 |
| KR20080107316A (en) | 2008-12-10 |
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Granted publication date: 20111012 Termination date: 20200605 |