CN101029154B - Halogen free flame retardant resin composition and wire cable using same - Google Patents
Halogen free flame retardant resin composition and wire cable using same Download PDFInfo
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- CN101029154B CN101029154B CN2007100861161A CN200710086116A CN101029154B CN 101029154 B CN101029154 B CN 101029154B CN 2007100861161 A CN2007100861161 A CN 2007100861161A CN 200710086116 A CN200710086116 A CN 200710086116A CN 101029154 B CN101029154 B CN 101029154B
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Abstract
The objective of the present inventin is to provide a hal free fire resistant resin composition as well as wires and cables using same. Said fire resistant resin composition possesses the following performances: no performances degeneration occurs when metal hydroxides are added into polyolefine resins; the resin composition has low viscosity, with excellent constructional properties. Relative to 100 parts by weight of polyolefine resins, said hal free fire resistant resin composition contains 150-300 parts by weight of metal hydroxides, 20-50 parts by weight of 1,3,5-triazine derivatives, 0.1-5 parts by weight of fatty salts(metal)and 0.01-1 parts by weight of fattiness acidamide.
Description
Technical field
The present invention relates to halogen free flame retardant resin composition and use its electric wire.
Background technology
As the flame retardant resin composition of halide not, use be in polyolefin-based resins, to add metal hydroxidess such as magnesium hydroxide, aluminium hydroxide and the composition that obtains.These compositions, because burning the time does not produce toxic gases such as hydrogenchloride Huo dioxin, the generation of poisonous gas or prevent secondary disaster etc. in the time of therefore can preventing fire is even and carry out burning disposal when scrapping and also problem can not take place.But, little by the flame retardant effect that adds the metal hydroxides generation, the addition of the usually flame retardant resistance that can not obtain expecting, thereby increase metal hydroxides.Accompany therewith, the resin combination high viscosityization, the load to forcing machine when making electric wire increases, and with respect to the resin combination of halide not, operation (extruded velocity etc.) is very poor.
[patent documentation 1] spy opens flat 9-1689 communique
[patent documentation 2] spy opens the 2000-178386 communique
[patent documentation 3] spy opens the 2000-195336 communique
[patent documentation 4] spy opens the 2000-129049 communique
Summary of the invention
The problem that invention will solve
In the technology in the past,, there is the problem of declines such as extruded velocity along with the increase of metal hydroxides addition.
In order to improve this problem, carry out lowering viscousity by adding metallic soaps such as low viscosity resin such as polyethylene wax or Zinic stearas.
But, when adding low viscosity resin, then can not get effect of sufficient on a small quantity, volume then descends relevant with characteristics such as tensile strength, flame retardant resistances.
When adding metallic soap in addition, then can not get effect of sufficient on a small quantity, volume then causes electric wire surface frosting or extrudes the bad of outward appearance.
Further, shown in patent documentation 1～4, propose to add pyrrolotriazine derivatives or fatty acid metals such as trimeric cyanamide cyanurate, but do not obtain the composition of good works such as keeping flame retardant resistance and extrude.
Therefore, the objective of the invention is, solve above-mentioned problem, the electric wire that halogen free flame retardant resin composition is provided and uses it, when described halogen free flame retardant resin composition adds metal hydroxides in polyolefin-based resins, occurrence features does not descend, the resin combination lowering viscousity, and operation is good.
The scheme of dealing with problems
In order to achieve the above object, the invention of claim 1 is a halogen free flame retardant resin composition, it is characterized by, with respect to polyolefin-based resins 100 weight parts, contain metal hydroxides 150～300 weight parts, 1,3,5-pyrrolotriazine derivatives 20～50 weight parts, fatty acid metal salt 0.1～5 weight part and fatty amide 0.01～1 weight part.
The invention of claim 2 is the described halogen free flame retardant resin composition of claim 1, wherein, polyolefin-based resins is more than select from the group of compositions such as new LDPE (film grade), straight chain shape new LDPE (film grade), straight chain shape ultra-low density polyethylene, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, ethene-copolymer-maleic anhydride, toxilic acid grafting straight chain shape new LDPE (film grade) at least a.
The invention of claim 3 is the described halogen free flame retardant resin composition of claim 1, wherein, polyolefin-based resins is the ethylene-ethyl acrylate copolymer (EEA) of 15～35wt% by the EA amount, and perhaps vinyl acetate content (VA amount) is ethylene-vinyl acetate copolymer (EVA) formation of 15～45wt%.
The invention of claim 4 is the described halogen free flame retardant resin composition of claim 1, and wherein, the 1,3,5-triazines derivative is selected from trimeric cyanamide, tricyanic acid, cyamelide, trimeric cyanamide cyanurate, sulfuric acid trimeric cyanamide.
The invention of claim 5 is the described halogen free flame retardant resin composition of claim 1, wherein, fatty acid metal salt is more than one that select from the group that Metallic stearates, 12-oxystearic acid metal-salt, montanic acid metal-salt, docosoic metal-salt and lauric acid metal-salt are formed.
The invention of claim 6 is the described halogen free flame retardant resin composition of claim 1, wherein, fatty amide is more than one that select from the group that stearic amide, amine hydroxybenzene, erucicamide, behenamide, N-oleyl (oleyl) palmitic amide, N-stearyl erucicamide, ethylenebis stearic amide, stearic acid diamide, oleic acid diamide, erucic acid diamide He docosoic diamide are formed.
The invention of claim 7 is an electric wire, it is characterized by, and uses each described halogen free flame retardant resin composition of the requirement 1～6 of having the right in the isolator of conductor or sheath.
The invention effect
According to halogen free flame retardant resin composition of the present invention, by and with fatty acid metal salt 0.1～5 weight part and fatty amide 0.01～1 weight part, the electric wire of the halogen free flame retardant resin composition of can obtain that service performance does not reduce in isolator, sheath, resin combination lowering viscousity, operation are good.
Description of drawings
Fig. 1 uses the sectional view that coats the cable that 3 bar insulation core peripheries form with twining package tape and sheath of the present invention.
Fig. 2 uses the sectional view that coats the electric wire that forms on copper conductor with isolator of the present invention.
Fig. 3 uses the sectional view that coats the cable that the core periphery of 4 twisted pair wires forms with the double layer rubber sleeve layer of the present invention.
Nomenclature
1 copper conductor
2 isolators
3 sheaths
Embodiment
Below, with reference to accompanying drawing of the present invention one suitable embodiment is elaborated.
At first, according to Fig. 1～Fig. 3, used the electric wire of halogen free flame retardant resin composition to describe to the present invention.
Fig. 1 represents that 3 cores that will coat isolator 2 on copper conductor 1 are stranded with weighting material 4, apply twining package tape, and extruding coats and the cable of formation as outermost layer with sheath 3, and sheath 3 is made by halogen free flame retardant resin composition of the present invention.
Fig. 2 represents that copper conductor 1 insulated body 2 coats the electric wire that forms, and isolator 2 is made by halogen free flame retardant resin composition of the present invention.
Fig. 3 represents, as insulated wire cores 6, its pair twist obtained twisted pair wire 7 with the thing of copper conductor 1 insulated body 2 coatings, with 4 twisted pair wires, the 7 stranded cores 8 that obtain, with the skin of this core 8 as sheath internal layer 9 and sheath outer 10 and extruding coats and forms article.Sheath internal layer 9 and sheath skin 10 are made by halogen free flame retardant resin composition of the present invention.
Polyolefin-based resins as the present invention's use, can enumerate new LDPE (film grade), straight chain shape new LDPE (film grade), straight chain shape ultra-low density polyethylene, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-styrene copolymer, ethene-copolymer-maleic anhydride, toxilic acid grafting straight chain shape new LDPE (film grade), more preferably ethylene-vinyl acetate copolymer.These can use a kind, or mix more than 2 kinds and use.
Ethylene-ethyl acrylate copolymer (EEA) is, preferred EA amount is 15～35wt%, and ethylene-vinyl acetate copolymer (EVA) is that preferred vinyl acetate content (VA amount) is 15～45wt%.
As metal hydroxides, these metal hydroxidess of nickel of can having enumerated magnesium hydroxide, aluminium hydroxide, calcium hydroxide and solid solution.These may be used alone, two or more kinds can also be used.In addition, these metal hydroxidess, also can use by silane coupling agent, titanic acid ester is that lipid acid such as coupling agent, stearate or calcium stearate or fatty acid metal salt etc. have carried out the surface-treated material.
Among the present invention, the addition of metal hydroxides is, can not obtain sufficient flame retardant resistance when 150～300 weight parts, addition are less than 150 weight parts, and during more than 300 weight parts, mechanical characteristics significantly descends.Preferred scope is 200～240 weight parts.
As the 1,3,5-triazines derivative, can enumerate trimeric cyanamide, tricyanic acid, cyamelide, trimeric cyanamide cyanurate, sulfuric acid trimeric cyanamide.More preferably trimeric cyanamide cyanurate.They also can carry out surface treatment by nonionogenic tenside or various coupling agent.
Among the present invention, the 1,3,5-triazines derivative is 20～50 weight parts, can not obtain sufficient flame retardant resistance when addition is less than 20 weight parts, and physical strength significantly descends during more than 50 weight parts.Preferred scope is 20～40 weight parts.
The 1,3,5-triazines derivative, in decomposing more than 300 ℃, distillation produces non-flammable gases, therefore thinks that it helps flame retardant resistance during burning.
As fatty acid metal salt, can enumerate Metallic stearates (Ca, Zn, Mg, Al, Ba, Li, Na, K), 12-oxystearic acid metal-salt (Ca, Zn, Mg, Al, Ba, Li, Na), montanic acid metal-salt (Ca, Zn, Mg, Al, Li, Na), docosoic metal-salt (Ca, Zn, Mg, Li, Na, Ag), lauric acid metal-salt (Ca, Zn, Ba, Li), more preferably 12-oxystearic acid metal-salt.These may be used alone, two or more kinds can also be used.Among the present invention, the addition of fatty acid metal salt is 0.1～5 weight part, and viscosity reduced insufficiently when addition was less than 0.1 weight part, can not obtain sufficient flame retardant resistance during more than 5 weight parts, caused bad order.0.4 weight part more preferably.
As fatty amide, can enumerate stearic amide, amine hydroxybenzene, erucicamide, behenamide, N-oleyl palmitic amide, N-stearyl erucicamide, ethylene bis-stearamide, stearic acid diamide, oleic acid diamide, erucic acid diamide, docosoic diamide, more preferably oleic acid diamide.These may be used alone, two or more kinds can also be used.
Among the present invention, the addition of fatty amide is 0.01～1 weight part, and viscosity reduced insufficiently when addition was less than 0.01 weight part, to the bill of material face creamization, flame retardant resistance was descended during more than 1 weight part.0.1 weight part more preferably.
In addition, except that above-mentioned Synergist S-421 95, can also add antioxidant, inorganic filler as required, melt additives such as agent, stablizer, carbon black, tinting material mutually.
Further, also can utilize organo-peroxide crosslinked, utilize the electron rays isoradial crosslinked.
Embodiment
Embodiments of the invention and comparative example are described.
As described below, make resin combination and cable.
Cooperation ratio with table 1, table 2 expression cooperates various compositions, with 40 ℃ of temperature of beginning, 190 ℃ of end temps, utilize the pressurization kneader carry out mixing after, mixing thing is made particle, with its isolator, push for 230 ℃ and make with thickness 0.41mm, design temperature as cable illustrated in fig. 2.
The evaluation of electric wire is judged by the following method.
(1) stretching experiment
According to the standard of JIS C3005, the electric wire of making is carried out stretching experiment.Elongation is less than 150% be designated as * (defective), is 150～300% to be designated as zero (qualified), and it is above is designated as ◎ (qualified and have nargin).Tensile strength is designated as * (defective) less than 10MPa's, is that 10～13MPa is designated as zero (qualified), and it is above is designated as ◎ (qualified and have nargin).
(2) flame retardant resistance experiment
According to the standard of UL subject 758, the electric wire of making is carried out vertical combustion experiment (VW-1).Judgement is, combustion time less than 30 seconds be designated as ◎ (qualified and have nargin), less than 1 minute zero (qualified) that be designated as, being designated as more than 1 minute * (defective).
(3) viscosity experiment
Use the smart mechanism of Japan to make made capillary viscosimeter (キ ヤ ピ ロ グ ラ Off) 1B and measure mixing composition granule.Under 230 ℃ of mensuration temperature, to the kapillary of long 5.0mm, external diameter 1.0mm, with velocity of shear 6.1 * 10
3(sec
-1) viscosity when measuring the extruding particle.With do not add fatty acid metal salt, fatty amide is compared, 2 one-tenth of viscosity degradation are above is designated as zero (qualified), less than 2 one-tenth be designated as * (defective).
(4) outward appearance
The surface and the cross section of the electric wire of making of 50 times observation by light microscope, shaggy, see frostization on the surface with being designated as * (defective) of foaming in the cross section, surperficial and cross section does not have unusual zero (qualified) that be designated as.
The embodiment that uses resin combination of the present invention to make is as shown in table 1.
The addition of the magnesium hydroxide among the embodiment 1,2 becomes under the situation of 150 weight parts (embodiment 1), 300 weight parts (embodiment 2), the tensile properties when addition of magnesium hydroxide increases (elongation) variation, therefore preferred magnesium hydroxide addition is less than 300 weight parts.
Do not have among the embodiment 5 of embodiment 4 and solid solution nickel hydroxide of magnesium hydroxide of solid solution nickel hydroxide, the flame retardant resistance of solid solution nickel hydroxide improves, and suits.
In addition, the 1,3,5-triazines derivative being changed into the embodiment 7 of sulfuric acid trimeric cyanamide, change among the embodiment 8 of trimeric cyanamide cyanurate, do not find the difference on the characteristic, all is good.In addition, for separately and used the embodiment 8,9 of fatty acid metal salt and fatty amide, characteristic is good.
Relative therewith, comparative example 1～8 is as shown in table 2.
[table 2]
(use level: weight part)
*1 weight Yi Enmagu (Off ア イ Application マ グ) SNE: terraced em Ji (テ イ one エ system ジ one) (strain)
*2MC-640: daily output chemistry (strain)
*3CS-6: day east changes into industry (strain)
*4 Si Lipakusi (ス リ パ Star Network ス) O: Japan changes into (strain)
*5AO-18: rising sun electrochemical industry (strain)
As shown in table 2, the addition of metal hydroxides is less than the comparative example 1,1 of specified amount, 3, the 5-pyrrolotriazine derivatives is less than the addition of comparative example 3, fatty acid metal salt of specified amount more than the addition of the comparative example 6 of specified amount and the fatty amide comparative example 8 more than specified amount, and flame retardant resistance is insufficient.For comparative example 6, comparative example 8, except flame retardant resistance is insufficient, bad order takes place also.
In addition, the addition of metal hydroxides is more than the comparative example 2 of specified amount, the 1,3,5-triazines derivative comparative example 4 more than specified amount, and elongation characteristics is insufficient.The addition of fatty acid metal salt is less than the comparative example 5 of specified amount and the comparative example 7 that the fatty amide addition is less than specified amount, and lowering viscousity is insufficient.
Claims (7)
1. low viscosity halogen free flame retardant resin composition, it is characterized by,, contain metal hydroxides 150～300 weight parts, 1 with respect to polyolefin-based resins 100 weight parts, 3,5-pyrrolotriazine derivatives 20～50 weight parts, fatty acid metal salt 0.1～5 weight part and fatty amide 0.01～1 weight part;
Above-mentioned fatty acid metal salt is more than one that select from the group that Metallic stearates, 12-oxystearic acid metal-salt, montanic acid metal-salt, docosoic metal-salt and lauric acid metal-salt are formed;
Above-mentioned fatty amide is more than one that select from the group that stearic amide, amine hydroxybenzene, erucicamide, behenamide, N-oleyl palmitic amide, N-stearyl erucicamide, ethylene bis-stearamide, stearic acid diamide, oleic acid diamide, erucic acid diamide He docosoic diamide are formed.
2. halogen free flame retardant resin composition according to claim 1, wherein, polyolefin-based resins is more than select from the group that straight chain shape new LDPE (film grade), straight chain shape ultra-low density polyethylene, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-styrene copolymer, ethene-copolymer-maleic anhydride and toxilic acid grafting straight chain shape new LDPE (film grade) are formed at least a.
3. halogen free flame retardant resin composition according to claim 1, wherein, polyolefin-based resins is a new LDPE (film grade).
4. halogen free flame retardant resin composition according to claim 1, wherein, polyolefin-based resins is the ethylene-ethyl acrylate copolymer (EEA) of 15～35wt% or ethylene-vinyl acetate copolymer (EVA) formation that vinyl acetate content (VA amount) is 15～45wt% by EA amount.
5. halogen free flame retardant resin composition according to claim 1, wherein, the 1,3,5-triazines derivative is selected from trimeric cyanamide, tricyanic acid, cyamelide, trimeric cyanamide cyanurate, sulfuric acid trimeric cyanamide.
6. electric wire is characterized by, and uses each described halogen free flame retardant resin composition in the claim 1～5 in the isolator of conductor or sheath.
7. cable is characterized by, and uses each described halogen free flame retardant resin composition in the claim 1～5 in the isolator of conductor or sheath.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006058204 | 2006-03-03 | ||
| JP2006058204A JP4735340B2 (en) | 2006-03-03 | 2006-03-03 | Non-halogen flame retardant resin composition and electric wire / cable using the same |
| JP2006-058204 | 2006-03-03 |
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| Publication Number | Publication Date |
|---|---|
| CN101029154A CN101029154A (en) | 2007-09-05 |
| CN101029154B true CN101029154B (en) | 2011-02-02 |
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| CN (1) | CN101029154B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009084524A (en) * | 2007-10-03 | 2009-04-23 | Hitachi Cable Ltd | Halogen-free flame-retardant resin composition and electric wire/cable using the same |
| JP5167931B2 (en) * | 2008-04-30 | 2013-03-21 | 日立電線株式会社 | Non-halogen flame retardant resin composition and electric wire / cable using the same |
| JP5588660B2 (en) * | 2009-11-24 | 2014-09-10 | 矢崎総業株式会社 | Flame retardant resin composition |
| JP5527252B2 (en) * | 2010-02-25 | 2014-06-18 | 日立金属株式会社 | Non-halogen flame retardant resin composition and cable using the same |
| JP5532013B2 (en) * | 2011-05-19 | 2014-06-25 | 日立金属株式会社 | Non-halogen flame retardant resin composition, electric wire, and cable |
| CN104769032B (en) * | 2012-11-09 | 2017-08-04 | 三井—杜邦聚合化学株式会社 | Resin combination and formed body |
| CN103030873B (en) * | 2012-12-31 | 2015-04-15 | 上海至正道化高分子材料股份有限公司 | 1E-grade K1-type low-smoke halogen-free vulcanized crosslinked cable shield material for AP1000 nuclear power station and preparation method of cable shield material |
| JP2014214291A (en) * | 2013-04-30 | 2014-11-17 | 矢崎総業株式会社 | Resin composition and electric wire using the same |
| CN103265750B (en) * | 2013-05-24 | 2016-03-02 | 安徽长园智豪电力科技有限公司 | A kind of Ethylene-methyl acrylate cable sheath material and preparation method thereof |
| JP6021746B2 (en) * | 2013-06-14 | 2016-11-09 | 日立金属株式会社 | Non-halogen flame retardant wire |
| CN103819805B (en) * | 2014-01-21 | 2016-04-27 | 安徽容源材料有限公司 | A kind of halogen free flame retardant cable sheath material and preparation method thereof |
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| GB2119387A (en) * | 1982-04-26 | 1983-11-16 | Nat Distillers Chem Corp | Flame retardant crosslinked polyolefin insulation material |
| US4477523A (en) * | 1982-04-26 | 1984-10-16 | National Distillers And Chemical Corporation | Flame retardant crosslinked polyolefin insulation material |
| US4871787A (en) * | 1987-06-23 | 1989-10-03 | Hitachi Cable Ltd. | Flame retardant electrical insulating composition having antifungal action |
| CN1662629A (en) * | 2002-06-24 | 2005-08-31 | 旭电化工业株式会社 | Flame retarder composition and flame retardant resin composition containing the composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3632735B2 (en) * | 1998-10-29 | 2005-03-23 | 古河電気工業株式会社 | Insulating resin composition and insulated wire |
| JP2002201361A (en) * | 2000-12-28 | 2002-07-19 | Wakoo Jushi Kk | Flame-retardant resin composition |
| JP3829647B2 (en) * | 2001-05-14 | 2006-10-04 | 日立電線株式会社 | Non-halogen flame retardant insulated wire with excellent wire strip properties |
| JP2003277550A (en) * | 2002-03-27 | 2003-10-02 | Kanegafuchi Chem Ind Co Ltd | Flame-retardant resin composition |
| JP3821233B2 (en) * | 2003-05-07 | 2006-09-13 | 日立電線株式会社 | Non-halogen flame retardant insulated wire |
-
2006
- 2006-03-03 JP JP2006058204A patent/JP4735340B2/en active Active
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2007
- 2007-03-01 CN CN2007100861161A patent/CN101029154B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2119387A (en) * | 1982-04-26 | 1983-11-16 | Nat Distillers Chem Corp | Flame retardant crosslinked polyolefin insulation material |
| US4477523A (en) * | 1982-04-26 | 1984-10-16 | National Distillers And Chemical Corporation | Flame retardant crosslinked polyolefin insulation material |
| US4871787A (en) * | 1987-06-23 | 1989-10-03 | Hitachi Cable Ltd. | Flame retardant electrical insulating composition having antifungal action |
| CN1662629A (en) * | 2002-06-24 | 2005-08-31 | 旭电化工业株式会社 | Flame retarder composition and flame retardant resin composition containing the composition |
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|---|---|
| JP2007231240A (en) | 2007-09-13 |
| CN101029154A (en) | 2007-09-05 |
| JP4735340B2 (en) | 2011-07-27 |
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