CN1828783A - Non-halogen flame resistant wire and cable - Google Patents
Non-halogen flame resistant wire and cable Download PDFInfo
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- CN1828783A CN1828783A CN 200610056801 CN200610056801A CN1828783A CN 1828783 A CN1828783 A CN 1828783A CN 200610056801 CN200610056801 CN 200610056801 CN 200610056801 A CN200610056801 A CN 200610056801A CN 1828783 A CN1828783 A CN 1828783A
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- cable
- flame resistant
- halogen flame
- resistant wire
- electric wire
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Abstract
This invention provides non-halogen electric wire and cable those have both stiffness in flexure and mechanical strength. The electric wire 1 and cable 10 are covered with resin composition 3 and 6, and the resin composition 3 and 6 are composed by bending 100 relative weight shares mixed polymers and 30~50 weight shares metal hydroxides. Wherein the mixed polymers comprises 40~95 weight shares polyolefin and 60~5 weight shares ethylene interpolymers modified with maleic anhydride, and the modified alkene interpolymers are modified ethylene-propylene copolymers or modified ethylene-butylene copolymers.
Description
Technical field
The present invention relates to little non-halogen flame resistant wire of carrying capacity of environment and cable, particularly non-halogen flame resistant wire and cable about having taken into account pliability and mechanical strength.
Background technology
Do not use the little non-halogen flame resistant wire and the cable of carrying capacity of environment of polyvinyl chloride and halogenated flame retardant to be popularized fast in recent years as environment-friendly electric wire and cable.For these non-halogen flame resistant wire and cables in the past, as the crust of the insulator of electric wire or cable uses usually in polyolefin mixing a large amount of with the resin combination of magnesium hydroxide as the non-halogen fire retardant of representative.
And then, as one of nearest trend, require to have used the electric wire and cable of the resin combination that the non-halogen material by the pliability excellence constitutes.
Here, relevant with the application's invention prior art documentation ﹠ info is as described below.
[patent documentation 1] spy opens the 2004-256621 communique
[patent documentation 2] spy opens the 2004-196877 communique
Summary of the invention
In order to give pliability to electric wire and cable, can use rubber in resin combination matrix is soft material.But, because rubber is that the soft material mechanical strength is low, therefore need carry out the crosslinked mechanical strength that improves, the non-crosslinked based resin composition is difficult to be suitable for.
In addition, in order to carry out the recycling of electric wire and cable, it is desirable to not crosslinked resin composition.
Like this, use noncrosslinking resin combination and pliability and the mechanical strength of taking into account electric wire and cable is difficult.
Therefore, the object of the present invention is to provide non-halogen flame resistant wire and the cable of having taken into account pliability and mechanical strength.
The present invention finishes to achieve these goals, the invention of claim 1 is non-halogen flame resistant wire and cable, it is non-halogen flame resistant wire and the cable that is coated with resin combination, described resin combination forms by 100 weight portion mixed polymers are mixed 30～150 parts by weight of metal hydroxide, described mixed polymer is 40～95 weight portion polyolefin and 60～5 weight portions mixture with maleic anhydride modified vinyl copolymer, and the maleic anhydride modified vinyl copolymer of described usefulness is maleic acid modified ethylene propylene copolymer or the ethene improved butylene copolymer of maleic acid.
The invention of claim 2 is the non-halogen flame resistant wire and the cable of claim 1 record, and wherein, the average grain diameter of described metal hydroxides is smaller or equal to 0.5 μ m, and processing was carried out by methacrylic acid silane (メ Network リ Le シ ラ Application) in its surface.
The invention of claim 3 is the non-halogen flame resistant wire and the cable of claim 1 or 2 records, and its described resin combination that is covered is made in the non-crosslinked mode.
The invention of claim 4 is the non-halogen flame resistant wire and the cable of each record in the claim 1～3, and wherein, 10% modulus of described non-halogen flame resistant wire and cable is smaller or equal to 3MPa.
According to the present invention, can obtain having taken into account the non-halogen flame resistant wire and the cable of pliability and mechanical strength.
Description of drawings
Fig. 1 is for representing as a routine non-halogen flame resistant wire of preferred implementation of the present invention and the cross-sectional view of cable.
Symbol description
1 non-halogen flame resistant wire
2 conductors
3 insulators (resin combination)
6 crusts (resin combination)
10 non-halogen fire-retardant cables
Embodiment
Below, preferred implementation of the present invention is described.
The non-halogen fire-retardant resin combination that present embodiment relates to is that relative 100 weight portion mixed polymers mix 30～150 weight portions and form as the metal hydroxides of fire retardant, and described mixed polymer is 40～95 weight portion polyolefin and 60～5 weight portions mixture with maleic anhydride modified vinyl copolymer (maleic acid modified ethylenic copolymer).
As polyolefin, use high, medium and low density polyethylene, polypropylene, ethylene propylene copolymer, propylene diene hydrocarbon terpolymer, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, straight chain shape low density polyethylene (LDPE) (LLDPE), ultra-low density polyethylene, ethylene vinyl acetate copolymer, ethylene-butylene copolymer, ethylene methacrylic acid methyl terpolymer, POE, ethylene vinyl acetate copolymer (EVA) etc.
For electric wire and cable being given excellent pliability, as the special optimal ethylene propylene copolymer of polyolefin, propylene diene hydrocarbon terpolymer, ethylene-butylene copolymer, POE.
On the other hand, as maleic acid modified ethylenic copolymer, use by maleic anhydride modified as the ethylene propylene copolymer of soft polymer or the copolymer of ethylene-butylene copolymer (the ethene improved butylene copolymer of maleic acid modified ethylene propylene copolymer or maleic acid).
Above-mentioned maleic acid modified ethylene propylene copolymer is compared with the hard maleic acid polymer-modified (the maleic acid modified version of polyethylene, polypropylene, ethylene ethyl acrylate copolymer, ethylene vinyl acetate copolymer) that uses in the past with the ethene improved butylene copolymer of maleic acid, and its advantage is that flexibility is very excellent.
Make polyolefinic combined amount be the combined amount of 40～95 weight portions, maleic acid modified ethylenic copolymer be 60～5 weight portions be because, if combined amount less than 5 weight portions of maleic acid modified ethylenic copolymer, then with metal hydroxides bonding a little less than, electric wire and cable can not obtain sufficient mechanical.Be in addition because, if the combined amount of maleic acid modified ethylenic copolymer surpasses 60 weight portions, then the percentage elongation of electric wire and cable can reduce significantly.
As metal hydroxides, use magnesium hydroxide (Mg (OH)
2), aluminium hydroxide (Al (OH)
3), hydrotalcite, calcium aluminate hydrate, calcium hydroxide, barium hydroxide etc.As magnesium hydroxide, use synthetic magnesium hydroxide, pulverize brucite that natural crystal obtains, form the magnesium hydroxide etc. of solid solution with other elements such as Ni.
With respect to 100 weight portion mixed polymers, the combined amount that makes metal hydroxides be 30～150 weight portions be because, if combined amount less than 30 weight portions, then the anti-flammability of electric wire and cable is insufficient; If combined amount surpasses 150 weight portions, then the mechanical property of electric wire and cable can reduce significantly.
Metal hydroxides can for, for example average grain diameter is smaller or equal to 0.5 μ m, and processing was carried out by methacrylic acid silane in its surface.
If the average grain diameter of metal hydroxides surpasses 0.5 μ m, then particle diameter becomes big, and metal hydroxides is difficult to be evenly dispersed in the resin combination, and the mechanical strength of electric wire and cable can reduce, and adds thermal deformation and also can become greatly, therefore is preferably smaller or equal to 0.5 μ m.
In addition, compare with the silane coupling agent that vinyl silanes (PVC ニ Le シ ラ Application) etc. is general, the molecular weight of methacrylic acid silane (メ Network リ Le シ ラ Application) is big, has the long structure of straight chain shape.Can think that this length structure is compared with short structure, alleviation effects is big when being subjected to stress, and consequently characteristic such as hot strength and percentage elongation can improve.
After the metal hydroxides spraying or soaking into methacrylic acid silane, by making its drying, can be at the surface attachment methacrylic acid silane of metal hydroxides.In mixed polymer, mix this usefulness methacrylic acid silane and carried out the surface-treated metal hydroxides.
In addition, in the resin combination that present embodiment relates to, except mentioned component, also can add crosslinking coagent, flame retardant, antioxidant, lubricant, stabilizer, filler, colouring agent, silicone etc. aptly.
Then, a routine non-halogen flame resistant wire and the cable that present embodiment relates to is described.
As shown in Figure 1, the non-halogen flame resistant wire that present embodiment relates to (insulated electric conductor) 1 is, the insulator 3 that (periphery) lining is made of above-mentioned non-halogen fire-retardant resin combination on conductor 2, the electric wire that is made in the non-crosslinked mode.
In addition, the non-halogen fire-retardant cable 10 that present embodiment relates to is, in the periphery of the core 5 that 2 insulated electric conductors arranged side by side 1 and field trash 4 are constituted sth. made by twisting simultaneously, the crust 6 that lining is made of above-mentioned non-halogen fire-retardant resin combination, the cable that is made in the non-crosslinked mode.Being generally used for the cooperation of the cooperation of resin combination of insulator 3 and the resin combination that is used for crust 6, some is different, and details is described in the back.
This cable 10 can be as for example circular or flat elevator cable, cabtyre cable.As conductor 2, use the single line of the twisting thread of Cu for example or Cu alloy, Cu or Cu alloy.As field trash 4, use for example polypropylene.
Below, the effect of present embodiment is described.
For electric wire 1 and cable 10, as insulator 3 and crust 6 use cooperated as the maleic acid of soft cementability polymer ethene improved-propylene copolymer or maleic acid be ethene improved-resin combination of butylene copolymer.Therefore, cooperated the electric wire and cable of the polymer-modified resin combination in the past of the maleic acid of hard to compare with use, very soft, can improve pliability significantly.
For example in embodiment described later, for electric wire 1 and cable 10, as 10% modulus (hot strength during 10% percentage elongation) of pliability index all smaller or equal to 3MPa.
In addition, the average grain diameter of metal hydroxides is little to be arrived smaller or equal to 0.5 μ m, and metal hydroxides is evenly dispersed in the resin combination, so the raising of the mechanical strength of electric wire 1 and cable 10, and it is also little to add thermal deformation.When making electric wire 1 and cable 10, the outward appearance of extruding of resin combination also becomes good.
And then electric wire 1 and cable 10 is because the polymer-modified metal hydroxides of crossing by the methacrylic acid silane treatment to each other of bonding polyolefinic maleic acid is crosslinked by vacation, even therefore non-crosslinked also has sufficient mechanical.
Thereby electric wire 1 and cable 10 can be taken into account mechanical strength (hot strength) and pliability.
When electric wire and cable requires high flame retardant, need in mixed polymer, mix a large amount of metal hydroxidess, even but mechanical strength reduces also few in this case.
The resin combination that present embodiment relates to is not limited to electric wire 1 and the cable 10 of Fig. 1, also can be as the handrail of for example escalator, the tail rope that elevator is used, fire-retardant film.
Embodiment
Embodiment (electric wire) 1～5
Polymer shown in the table 1, antioxidant, fire retardant, packing material input remained on carry out mixingly in 100～130 ℃ the mixing roll (8 inches unlimited rollers), use the 40mm extruder (L/D=24) that remains on 180 ℃ to be 2mm at sectional area with thickness 1mm
2Copper twist thread and extrude the resin combination of lining after mixing on (conductor 2), form insulator 3, with the insulated electric conductor 1 of non-crosslinked mode construction drawing 1.
Embodiment (cable) 6～8
On the core 5 that insulated electric conductor 1 and polypropylene field trash 4 with embodiment 3 obtain sth. made by twisting simultaneously, use remains on 180 ℃ 40mm extruder (L/D=24) and extrudes the resin combination that the polymer shown in the lining table 1, antioxidant, fire retardant, packing material constitute, form crust 6, with the cable 10 of non-crosslinked mode construction drawing 1.
Comparative example (electric wire) 1～4
Use the resin combination of the cooperation shown in the table 1, similarly make insulated electric conductor with embodiment 1～5.
The evaluation method of each electric wire and cable is carried out with following method.
(1) tensile properties
At electric wire, use the pipe of extracting conductor out and obtaining to carry out tension test according to JIS C3005.In addition,, strip crust, and it is cut into dumbbell No. 3, carry out tension test according to JIS K6251 at cable.Draw speed is 200mm/min.The target of hot strength and percentage elongation is respectively more than or equal to 10MPa, more than or equal to 350%.
(2) pliability: 10% modulus
For pliability, use Tan Xilun (single strand tester) to carry out tension test with the same sample of making of above-mentioned tension test according to JIS K6251 pair, the mensuration percentage elongation is 10% o'clock a hot strength.Draw speed is 200mm/min.Flexual target is smaller or equal to 3.0MPa.
(3) add thermal deformation
At electric wire, be the tabular of width 15mm, length 30mm, thickness 2mm with the composition molding identical with the insulator quality, with this as sample, according to JIS C3005 75 ℃ of load that apply 1.5kg.At cable, take the sample of length 30mm from finished product, make inner face level and smooth, carry out same test with electric wire.It is qualified that deflection is set at smaller or equal to 10%.
(4) anti-flammability
Anti-flammability when estimating 60 ° of inclinations according to JIS C3005 at each electric wire and cable.The benchmark of estimating is, being set at of confirming that the back extinguishes in smaller or equal to 60 seconds of catching fire is qualified, and it is defective to surpass being set at of burning away in 60 seconds.
The cooperation and the evaluation result thereof of the resin combination of each electric wire and cable of embodiment 1～5, embodiment 6～8, comparative example 1～4 are shown in Table 1.Use level in the table 1 is represented with weight portion.
Table 1
| Kind | Embodiment (electric wire) | Embodiment (cable) | Comparative example (electric wire) | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 1 | 2 | 3 | 4 | |||
| Cooperate | Polymer | Propylene diene hydrocarbon terpolymer (EP21, JSR society system) | 65 | 50 | 50 | 40 | 30 | 30 | 20 | 45 | 100 | 45 | 45 | |
| Ethylene propylene copolymer ( Off マ DF810, Mitsui Chemicals society system) | 30 | 35 | ||||||||||||
| Ethylene-butylene copolymer ( Off マ DF9200, Mitsui Chemicals society system) | 30 | |||||||||||||
| Ethylene-butylene copolymer ( Off マ DF9700, Mitsui Chemicals society system) | 10 | 10 | 15 | 15 | 15 | |||||||||
| LLDPE (density 0.921, comonomer: propylene) | 10 | 20 | ||||||||||||
| EVA (VA amount 33%, MFR0.2) | 10 | 40 | ||||||||||||
| The ethene improved butylene copolymer of maleic acid ( Off マ MH7020, Mitsui Chemicals society system) | 5 | 20 | 40 | 40 | 60 | 40 | 65 | 40 | 40 | |||||
| Maleic acid modified ethylene propylene copolymer ( Off マ MP0620, Mitsui Chemicals society system) | 30 | 60 | ||||||||||||
| Antioxidant | イ Le ガ ノ Star Network ス 1010 (チ バ ガ イ ギ one society's system) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
| Fire retardant | Magnesium hydroxide (methacrylic acid silane treatment, average grain diameter 0.3 μ m) | 40 | 60 | 150 | 50 | 40 | 60 | 60 | ||||||
| Magnesium hydroxide (vinyl silanes processing, average grain diameter 0.3 μ m) | 30 | 60 | ||||||||||||
| Magnesium hydroxide (vinyl silanes processing, average grain diameter 1.0 μ m) | 50 | 25 | ||||||||||||
| Magnesium hydroxide (stearic acid processing, average grain diameter 1.0 μ m) | 60 | 95 | ||||||||||||
| Packing material | Calcium carbonate (stearic acid processing, average grain diameter 0.1 μ m) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Evaluation result | Hot strength (MPa) target 〉=10 | 12.6 | 13.6 | 11.4 | 10.8 | 11.5 | 13.2 | 11.6 | 12.4 | 6.2 | 16.7 | 7.8 | 9.2 | |
| Percentage elongation (%) target 〉=350 | 600 | 550 | 480 | 520 | 380 | 480 | 540 | 520 | 640 | 220 | 400 | 600 | ||
| Pliability 10% modulus (MPa) target≤3.0 | 1.5 | 1.8 | 2.2 | 2 | 2.8 | 1.9 | 2.2 | 1.3 | 1 | 2.9 | 3.9 | 1.8 | ||
| Add (%) target≤10 of thermal deformation (75 ℃, 1.5kg) | 7.8 | 4.8 | 6.9 | 9.2 | 6.6 | 7.8 | 9.6 | 8.1 | 18 | 6.4 | 8.8 | 9.8 | ||
| Anti-flammability (JIS inclination) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Defective | ||
As shown in table 1, among the embodiment 1～5, the polymer-modified ratio of polyolefin and soft maleic acid is in prescribed limit of the present invention, and hot strength is 10.8～13.6MPa, and percentage elongation is 380～600%, all reaches target, and tensile properties is good.And 10% modulus is 1.5～2.8MPa, all reaches target, pliability excellence not only, and also it is little to add thermal deformation, and anti-flammability is also excellent.
And embodiment 6～8 is also same with embodiment 1～5, and hot strength is 12.4～13.2MPa, and percentage elongation is 480～540%, all reaches target, and tensile properties is good.And 10% modulus is 1.3～2.2MPa, all reaches target, pliability excellence not only, and also it is little to add thermal deformation, and anti-flammability is also excellent.
In contrast, comparative example 1 does not use maleic acid polymer-modified because mixed polymer only is made of the rubber based material, even therefore the average grain diameter handled of mixed methyl acrylic silane is the magnesium hydroxide of 0.3 μ m, hot strength is also low, and it is also big to add thermal deformation.
Comparative example 2 is because maleic acid is polymer-modified outside prescribed limit of the present invention, so percentage elongation is low.Comparative example 3 exceed prescribed limit of the present invention, so hot strength is low, and then pliability is damaged also because the combined amount of magnesium hydroxide is 155 weight portions.Comparative example 4 is because magnesium hydroxide is few, so anti-flammability is defective.
Claims (4)
1. non-halogen flame resistant wire and cable, it is characterized in that, it is non-halogen flame resistant wire and the cable that is coated with resin combination, described resin combination forms by 100 weight portion mixed polymers are mixed 30～150 parts by weight of metal hydroxide, described mixed polymer is 40～95 weight portion polyolefin and 60～5 weight portions mixture with maleic anhydride modified vinyl copolymer, and the maleic anhydride modified vinyl copolymer of described usefulness is maleic acid modified ethylene propylene copolymer or the ethene improved butylene copolymer of maleic acid.
2. according to the non-halogen flame resistant wire and the cable of claim 1 record, it is characterized in that the average grain diameter of described metal hydroxides is smaller or equal to 0.5 μ m, and processing was carried out by methacrylic acid silane in its surface.
3. according to the non-halogen flame resistant wire and the cable of claim 1 or 2 records, it is characterized in that its described resin combination that is covered is made in the non-crosslinked mode.
4. according to the non-halogen flame resistant wire and the cable of each record in the claim 1～3, it is characterized in that 10% modulus of described non-halogen flame resistant wire and cable is smaller or equal to 3MPa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005060386 | 2005-03-04 | ||
| JP2005060386A JP2006244894A (en) | 2005-03-04 | 2005-03-04 | Nonhalogen flame-retardant electric wire and cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1828783A true CN1828783A (en) | 2006-09-06 |
| CN100580820C CN100580820C (en) | 2010-01-13 |
Family
ID=36947100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610056801A Expired - Fee Related CN100580820C (en) | 2005-03-04 | 2006-03-03 | Non-halogen flame resistant wire and cable |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006244894A (en) |
| CN (1) | CN100580820C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323689B (en) * | 2007-06-13 | 2011-04-13 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
| CN101359520B (en) * | 2007-06-05 | 2011-10-12 | 住友电气工业株式会社 | Non-halgen flame retardant wire |
| CN101685684B (en) * | 2008-09-27 | 2012-05-23 | 中利科技集团股份有限公司 | Copper-clad aluminum flexible cable and manufacture method thereof |
| CN103700439A (en) * | 2012-09-27 | 2014-04-02 | 日立金属株式会社 | Non-halogen flame-retardant insulated wire |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3052273B2 (en) * | 1993-03-25 | 2000-06-12 | 日立電線株式会社 | Flame retardant electrical insulating composition and insulated wire |
| JPH10255560A (en) * | 1997-03-10 | 1998-09-25 | Hitachi Cable Ltd | Flame retardant wire and cable |
| JP2001160316A (en) * | 1999-12-03 | 2001-06-12 | Hitachi Cable Ltd | Nonhalogen flame-resistant electric cable |
| JP3759699B2 (en) * | 2001-01-19 | 2006-03-29 | 住友電装株式会社 | Olefin resin composition and coated electric wire |
-
2005
- 2005-03-04 JP JP2005060386A patent/JP2006244894A/en active Pending
-
2006
- 2006-03-03 CN CN200610056801A patent/CN100580820C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101359520B (en) * | 2007-06-05 | 2011-10-12 | 住友电气工业株式会社 | Non-halgen flame retardant wire |
| CN101323689B (en) * | 2007-06-13 | 2011-04-13 | 日立电线株式会社 | Non-halogen flame retardant resin composition and non-halogen flame retardant electric wire and cable |
| CN101685684B (en) * | 2008-09-27 | 2012-05-23 | 中利科技集团股份有限公司 | Copper-clad aluminum flexible cable and manufacture method thereof |
| CN103700439A (en) * | 2012-09-27 | 2014-04-02 | 日立金属株式会社 | Non-halogen flame-retardant insulated wire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006244894A (en) | 2006-09-14 |
| CN100580820C (en) | 2010-01-13 |
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