CN101245166B - Flame-proof soft vinyl plastics for electric wire and cable - Google Patents
Flame-proof soft vinyl plastics for electric wire and cable Download PDFInfo
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- CN101245166B CN101245166B CN2008100207675A CN200810020767A CN101245166B CN 101245166 B CN101245166 B CN 101245166B CN 2008100207675 A CN2008100207675 A CN 2008100207675A CN 200810020767 A CN200810020767 A CN 200810020767A CN 101245166 B CN101245166 B CN 101245166B
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Abstract
The invention relates to a piece of inflaming retarding soft polyvinyl chloride plastic used in electric wires and cables, which belongs to sheath and insulation materials used in electric wires and cables in industrial polymer materials and is composed of the raw materials with the following proportion by weight: 25 to 70 parts by weight of polyvinyl chloride resin 100 plasticizer; 5 to 40 partsby weight of co-polymerization resin, 3 to 12 parts by weight of stabilizing agent; 5 to 20 parts by weight of flame retardant I; 5 to 25 parts by weight of flame retardant II; 30 to 130 parts by weight of flame retardant III; 0 to 40 parts by weight of loading agent and 0.5 to 5 parts by weight of lubricant. The inflaming retarding soft polyvinyl chloride plastic used in electric wires and cablesprovided by the invention has very good inflaming retarding performance with the oxygen index as high as more than 46 and can meet the requirements of using the electric wires and cables with specialinflaming retarding requirements as the sheath and insulation materials; the inflaming retarding soft polyvinyl chloride plastic not only has very good inflaming retarding performance but also has favorable low temperature resistant and embrittlement resistant performances and very good soft performance and processing performance.
Description
Technical field
The invention belongs to electric wire sheath and insulating material in the industrial macromolecular material, more specifically say it is a kind of flame-proof soft vinyl plastics for electric wire and cable.
Background technology
Soft polyvinyl chloride plastic has good physical mechanical electric property, is fit to do the insulation and the sheath material of low tension wire cable.In special use occasion, electric wire is had higher fire-retardant requirement, as UL1666 (propagation of flame of cable height in the vertical shaft), UL910 (spreading and the measurement of smoke density of cable flame), category-A among the TEL60332-3-22 (the vertical propagation of fire test of the bunchy electric wire of vertically laying) etc.Oxygen index is used to evaluate the Flame Retardancy energy, and oxygen index high flame resistance more is good more.For example export digital cable and can propose oxygen index more than 39 or the requirement of 45 above high flame retardants to soft PVC plastic for electric wire and cable need be by standards such as UL1666 or UL910 the time.
The oxygen index of polyvinyl chloride (PVC) RESINS is 45, but it is a mechanically resistant material.Being used for electric wire is the soft polyvinyl chloride plastic that certain flexibility is arranged, and promptly needs to add a certain amount of softening agent in polyvinyl chloride (PVC) RESINS, to reach soft and low temperature resistant requirement.Yet softening agent is generally combustible matl, so the oxygen index of soft polyvinyl chloride plastic declines to a great extent, is 22～25.General soft polyvinyl chloride plastic is made fire retardant by adding antimonous oxide, can make the material oxygen index reach 30～32.But further improve difficulty, reach 35 very difficult, reach 40 or more even difficulty very more than 45, even possibility hardly.
Chinese patent publication number CN1676546A has introduced a kind of fire retardant mine soft cable igelite, and its disclosed weight proportion is:
High DP PVC 100;
Low polymerization degree PVC 10～50;
Softening agent 60～120;
Lead sulfate tribasic 2～5;
Dibasic lead phosphite 2～5;
Dibasic lead stearate 0.5～1.5;
Barium stearate 0.5～1.0;
Main flame retardant 10～20;
Auxiliary flame retardant 2～7;
Oxidation inhibitor 0.1～1.0;
Weighting agent 10～30.
Its main flame retardant is an antimonous oxide, and auxiliary flame retardant is a molybdenum oxide.The electric wire product requires lower unit cable testing vertical flammability by flame retardant rating, and the resilient material oxygen index is about about 30.
Chinese patent publication number CN 1752133A has introduced the fire retardant insulating grade polyvinyl chloride plastic that a kind of electric wire is used, and the fire retardant of recommendation is zinc borate, antimonous oxide and tetrabromo-bisphenol, and the oxygen index of plastics is 30.
Because the soft PVC plastic for electric wire and cable oxygen index of above-mentioned patent is 30, therefore all exist flame retardant properties general, can not satisfy the requirement of high flame retardant.
Summary of the invention
Task of the present invention is that a kind of more flame-proof soft vinyl plastics for electric wire and cable of excellent flame-retardant that has will be provided.
Task of the present invention is to finish like this, a kind of flame-proof soft vinyl plastics for electric wire and cable, and it is to be made of following raw materials in weight portion:
Polyvinyl chloride (PVC) RESINS 100;
Softening agent 25～70;
Copolymer resins 5～40;
Stablizer 3～12;
Fire retardant I 5～20;
Fire retardant II 5～25;
Fire retardant III 30～130;
Weighting agent 0～40;
Lubricant 0.5～5.
Polyvinyl chloride (PVC) RESINS of the present invention is any one resin in the resin of the polymerization degree 1000～1300 or SG1, SG2, SG3, the SG4 type resin.
Softening agent of the present invention is a kind of or its mixture in phthalic ester plasticizer, terephthalate class softening agent, the trimellitic acid ester plasticizer.
Copolymer resins of the present invention is the mixture of any one or ethylene-vinyl acetate terpolymer and ethylene-acrylate terpolymer in ethylene-vinyl acetate terpolymer or the ethylene-acrylate terpolymer.
Stablizer of the present invention is lead salt stabilizer or do not have lead stabilizer, perhaps the mixture of lead salt stabilizer and no lead stabilizer.
Fire retardant I of the present invention is the antimony based compound; Fire retardant II is the boracic fire retardant; Fire retardant III is the mixture of aluminium hydroxide or magnesium hydroxide or aluminium hydroxide and magnesium hydroxide.
Phthalic ester plasticizer of the present invention is any one or its mixture in the two undecyl alcohol esters of dioctyl phthalate (DOP), diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid, the two tridecanol esters of phthalic acid; Described terephthalate class softening agent is a dioctyl terephthalate; Described class softening agent trimellitate is any one or its mixture in trioctyl trimellitate, tri trimellitate ester in the ninth of the ten Heavenly Stems, the triisodecyl trimellitate.
Lead salt stabilizer of the present invention is any one in lead cyanurate, tribasic lead sulfate, dibasic Lead Phosphite, the lead silicate; Described no lead stabilizer is calcium-zinc composite stabilizing agent, rare earth class stablizer.
Antimony based compound of the present invention is antimonous oxide or antimony pentaoxide; Described boracic fire retardant is zinc borate, Sodium Tetraborate, barium metaborate.
Weighting agent of the present invention is one or more the mixture in lime carbonate, calcinated argil, potter's clay, silicate, the talcum powder; Described lubricant is any one or more than one the mixture in stearic acid and ester class thereof, stearates, polyethylene wax, paraffin, stearic amide, the amine hydroxybenzene.
Soft PVC plastic for electric wire and cable provided by the present invention has excellent flame-retardant, and oxygen index can reach more than 46, and the electric wire that can satisfy special fire-retardant requirement is done the service requirements of sheath or insulating material; Not only have excellent flame-retardant, and have good anti-low temperature brittleness performance, and have good softness and good processing properties.
Description of drawings
Accompanying drawing is depicted as with raw material disclosed in this invention and is processed into the process flow sheet that is extruded the particle that goes on the electric wire.
Embodiment
Following applicant is described in detail the present invention, to help the understanding of the present invention.
In the polyvinyl chloride (PVC) RESINS that the applicant recommended, SG1, SG2, SG3, SG4 type resin are meant the SG1 described in the GB/T 5761, SG2 in the CNS, SG3, SG4 type resin, and the polymerization degree is that 1000～1300 resin is meant that vinylchlorid is 1000～1300 resin for the monomer polymerization degree.
At the described softening agent of applicant,,, do not get rid of and do not lift not other ester class that belongs to phthalic acid in list that reaches though enumerated dioctyl phthalate (DOP) etc. as phthalic ester; With example, as the trimellitate class, though enumerated trioctyl trimellitate etc., as long as but belong to trimellitate class category, all should think row at list.
Based on above-mentioned reason, mentioned copolymer resins, stablizer, fire retardant, the lubricant of applicant is also right, all can not limit the body invention thus.
Embodiment 1
Composition weight part (consumption part)
Polyvinyl chloride resin (SG3 type) 100;
Trioctyl trimellitate (TOTM) 25;
Copolymer resins (Elvaloy 741) 40;
Lead cyanurate 8;
Antimonous oxide 20;
Zinc borate 25;
Aluminium hydroxide 30;
Lime carbonate 35;
Barium stearate 1.5.
Embodiment 2
Composition weight part (consumption part)
Polyvinyl chloride resin (polymerization degree is 1300) 100;
Trioctyl trimellitate (TOTM) 30;
Copolymer resins (Elvaloy HP551) 15;
Lead cyanurate 12;
Antimonous oxide 15;
Zinc borate 25;
Aluminium hydroxide 50;
Lime carbonate 10;
Lead stearate 1.2.
Embodiment 3
Composition weight part (consumption part)
Polyvinyl chloride resin (polymerization degree is 1300) 100;
Trioctyl trimellitate (TOTM) 32;
Di Iso Decyl Phthalate (DIDP) 10;
Copolymer resins (Elvaloy HP551) 20;
Lead cyanurate 4;
Antimonous oxide 10;
Zinc borate 15;
Aluminium hydroxide 120;
Lead stearate 1.5;
Barium stearate 1;
Stearic amide 0.5.
Embodiment 4
Composition weight part (consumption part)
Polyvinyl chloride resin (SG2 type) 100;
Trioctyl trimellitate (TOTM) 20;
Di Iso Decyl Phthalate (DIDP) 5;
Copolymer resins (Elvaloy HP551) 30;
Calcium-zinc composite stabilizing agent 8;
Antimonous oxide 5;
Zinc borate 15;
Aluminium hydroxide 70;
Magnesium hydroxide 20;
Stearic amide 0.6.
Embodiment 5
Composition weight part (consumption part)
Polyvinyl chloride resin (polymerization degree is 1300) 100;
Trioctyl trimellitate (TOTM) 50;
Copolymer resins (Elvaloy HP551) 10;
Lead cyanurate 3;
Antimonous oxide 20;
Zinc borate 20;
Aluminium hydroxide 120;
PE wax 0.5;
Lead stearate 1.5.
Embodiment 6
Composition weight part (consumption part)
Polyvinyl chloride resin (polymerization degree is 1300) 100;
Trioctyl trimellitate (TOTM) 65;
Copolymer resins (Elvaloy HP551) 5;
Lead cyanurate 6;
Antimonous oxide 15;
Zinc borate 20;
Aluminium hydroxide 130;
PE wax 0.5;
Stearic amide 1.
Embodiment 7
Composition weight part (consumption part)
Polyvinyl chloride resin (polymerization degree is 1300) 100;
Trioctyl trimellitate (TOTM) 20;
Dioctyl phthalate (DOP) (DOP) 5;
Copolymer resins (Elvaloy 741) 40;
Lead cyanurate 10;
Antimonous oxide 12;
Zinc borate 5;
Aluminium hydroxide 70;
Calcinated argil 20;
Calcium stearate 1.5.
The various components of the foregoing description 1 to 7 are mixed the back and are rolled mixing and plasticizing in the mill 160 ℃ two, pull into sheet after, depress to test piece at 170 ℃, test after being cut into sample.Their flame retardant properties and mechanical property see the following form:
Embodiment 1 to 7 has excellent flame-retardant, and oxygen index reaches more than 46, about 50.If adopt calcium-zinc composite stabilizing agent among the embodiment 4, embodiment 4 can use the ROSH instruction of objectionable impurities by restriction in European Union's electronic electric equipment.
Ask for an interview accompanying drawing, raw material according to the foregoing description, adopt processing process figure shown in the drawings, with the polyvinyl chloride (PVC) RESINS of being recommended, softening agent, stablizer, fire retardant, weighting agent, lubricant by the weight ratio of recommending, weighing preparation back adds in the high speed kneader, mediates kneading temperature to 100 ℃ 6～9 minutes, add copolymer resins then, mix to mediate after 1～2 minute and expect to put to cold kneader to stir discharging in 2～3 minutes; To mediate material and be added in the extruding granulator, the temperature of extrusion plasticizing and prilling temperature are controlled to be 130 ℃～150 ℃ respectively, make the flexible PVC particle with excellent fire-retardancy through plasticizing, granulation, cooling, packing.This pellet supply lines cable production firm directly is extruded in outside the electric wire core with extruding machine with conventional electric wire.This pellet has the physics shown in the following table, machinery and flame retardant properties after tested.
| Performance | Unit | Test value | Test method |
| Tensile strength | MPa | 13.1 | GB 1040 |
| Elongation at break | ％ | 220 | GB 1040 |
| Impact embrittlement temperature | -20℃ | By | GB 5470 |
| Thermal distortion | ％ | 20 | GB 8815 |
| 20 ℃ of volume specific resistances | Ω·m | 2.0×10 11 | GB 1410 |
| Dielectric strength | MV/m | 24 | GB 1408 |
| Oxygen index | - | 51 | GB 2406 |
| (100 ℃ * 240hr) the aging back of aging back draft intensity tensile strength retention rate elongation at break elongation retention rate of thermal ageings | MPa ％ ％ ％ | 14.5 111 210 95 | GB 8815 |
Claims (5)
1. flame-proof soft vinyl plastics for electric wire and cable is characterized in that it is to be made of following raw materials in weight portion:
Polyvinyl chloride (PVC) RESINS 100;
Softening agent 25～70;
Copolymer resins 5～40;
Stablizer 3～12;
Fire retardant I 5～20;
Fire retardant II 5～25;
Fire retardant III 30～130;
Weighting agent 0～40;
Lubricant 0.5～5,
Described softening agent is a kind of or its mixture in phthalic ester plasticizer, terephthalate class softening agent, the trimellitic acid ester plasticizer, described copolymer resins is the ethylene-acrylate terpolymer, described stablizer is no lead stabilizer or lead salt stabilizer, the mixture that does not perhaps have lead stabilizer and lead salt stabilizer, described fire retardant I is the antimony based compound; Fire retardant II is the boracic fire retardant; Fire retardant III is the mixture of aluminium hydroxide or magnesium hydroxide or aluminium hydroxide and magnesium hydroxide, and described antimony based compound is antimonous oxide or antimony pentaoxide; Described boracic fire retardant is a zinc borate.
2. flame-proof soft vinyl plastics for electric wire and cable according to claim 1 is characterized in that described polyvinyl chloride (PVC) RESINS is any one resin in the resin of the polymerization degree 1000～1300 or SG1, SG2, SG3, the SG4 type resin.
3. flame-proof soft vinyl plastics for electric wire and cable according to claim 1 is characterized in that described phthalic ester plasticizer is any one or its mixture in the two undecyl alcohol esters of dioctyl phthalate (DOP), diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid, the two tridecanol esters of phthalic acid; Described terephthalate class softening agent is a dioctyl terephthalate; Described trimellitic acid ester plasticizer is any one or its mixture in trioctyl trimellitate, tri trimellitate ester in the ninth of the ten Heavenly Stems, the triisodecyl trimellitate.
4. flame-proof soft vinyl plastics for electric wire and cable according to claim 1 is characterized in that described lead salt stabilizer is any one in lead cyanurate, tribasic lead sulfate, dibasic Lead Phosphite, the lead silicate; Described no lead stabilizer is calcium-zinc composite stabilizing agent, rare earth class stablizer.
5. flame-proof soft vinyl plastics for electric wire and cable according to claim 1 is characterized in that
Described weighting agent is one or more the mixture in lime carbonate, calcinated argil, potter's clay, silicate, the talcum powder; Described lubricant is any one or more than one the mixture in stearic acid and ester class thereof, stearates, polyethylene wax, paraffin, stearic amide, the amine hydroxybenzene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100207675A CN101245166B (en) | 2008-02-22 | 2008-02-22 | Flame-proof soft vinyl plastics for electric wire and cable |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100207675A CN101245166B (en) | 2008-02-22 | 2008-02-22 | Flame-proof soft vinyl plastics for electric wire and cable |
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| CN101245166A CN101245166A (en) | 2008-08-20 |
| CN101245166B true CN101245166B (en) | 2010-04-07 |
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| CN101245166A (en) | 2008-08-20 |
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Effective date of registration: 20180213 Address after: Changkun Industrial Park in Jiangsu province 215542 Changshou City Shajiabang town Co-patentee after: Jiangsu Zhongli group Limited by Share Ltd Patentee after: Changshu Zhonglian Photoelectricity New Stuff Co.,Ltd. Address before: Changkun Industrial Park in Jiangsu province 215542 Changshou City Shajiabang town Patentee before: Changshu Zhonglian Photoelectricity New Stuff Co.,Ltd. |