CN102276905A - Formulation of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product, and preparation method thereof - Google Patents
Formulation of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a formulation of a radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product, and a preparation method thereof. The formulation comprises, by mass, 20-40 parts of an ethylene vinyl acetate copolymer, 0-10 parts of an ethylene acrylate copolymer, 1-15 parts of a maleic anhydride graft polymer, 1-15 parts of silicone masterbatch, 10-20 parts of superfine surface treated active aluminium hydroxide, 10-20 parts of superfine surface treated active magnesium hydroxide, 1-10 parts of zinc borate, 0-10 parts of surface treated superfine red phosphorus, 0-10 parts of an organic nitrogen-phosphorus fire retardant, 0-5 parts of titanium dioxide, 0.2-1 parts of a lubricant, 0.5-1 parts of an antioxidant, 0.5-2 parts of a sensitized cross-linking agent, 0.5-2 parts of a light stabilizer and 1-5 parts of color master batch. The prepared identified casing product has performance of good fire retardant property, good mechanical property, good insulation property, good wear resistance, good corrosion resistance, good light aging resistance and the like. According to the present invention, the heat transfer printing is adopted; the handwriting is clear; the service life is more than 20 years; the identification has good wiping resistance and good solvent resistance; the product is easy to be used, and is bundled on the position of the large size cable requiring identification through the nylon binding tape; the mechanical property and the fire retardant property of the product are substantially improved due to the radiation cross-linking treatment.
Description
Technical field
The present invention relates to identify the sleeve technology field, particularly a kind of prescription and making method of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product.
Background technology
Use needs under special occasions and the mal-condition in order to satisfy, thermal contraction sign sleeve pipe has favorable mechanical, insulation, adopting heat to shift prints, writing is clear, surpass 20 years work-ing life, permanent identification, heat-proof aging, corrosion-resistant, good light stability, easy to use, and have good flame retardancy.Halogen containing polymers or have good flame retardant property with flame-retardant mixture that halogen containing flame-retardant combines, the Ceng Zuowei fire retardant material is widely used.When fire took place, this class Halogen fire retardant material can produce a large amount of smog and deleterious corrosive hydrogen halides gas, caused into secondary harm.New flame-retardant system, the amount of being fuming is little during burning, does not produce poisonous, corrosive gases.Fire retardant additive without halogen is mainly based on phosphorus series compound and metal hydroxides.This two compounds, non-volatile during burning, do not produce corrosive gases, be called as nuisanceless fire retardant.Common cross-linking radiation thermal contraction sign sleeve pipe discharges toxic and harmful when burning.
Summary of the invention
The invention provides a kind of prescription and making method with cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product of performances such as good fire-retardant, mechanical, insulation, wear-resisting, anticorrosive, anti-light aging.
To achieve these goals, the invention provides following technical scheme:
A kind of prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product, the ratio according to quality comprises:
Ethylene vinyl acetate copolymer EVA 20-40
Ethylene acrylate copolymer EEA 0-10
Maleic anhydride grafted polymer 1-15
Silicone master batch 1-15
Ultra-fine surface treatment active aluminium hydroxide 10-20
Ultra-fine surface treatment active hydrogen magnesium oxide 10-20
Zinc borate 1-10
Surface treatment ultra-fine red phosphorus 0-10
Organonitrogen phosphorus fire retardant 0-10
Titanium dioxide 0-5
Lubricant 0.2-1
Oxidation inhibitor 0.5-1
Sensitization linking agent 0.5-2
Photostabilizer 0.5-2
Look female 1-5.
Wherein, preferred, the propenyl acetate EA content of the vinylacetate VA of described EVA or EEA is respectively: 5-15%, melting index 1-10.0g/10min.
Wherein, preferred, described maleic anhydride grafted polymer comprises: low density polyethylene, ethylene vinyl acetate copolymer EVA and polyolefin elastomer POE, this maleic anhydride grafted polymer percentage of grafting is: 0.5-2.0%.
Wherein, preferred, described silicone master batch is: organo-siloxane extra high molecular polymer and carrier blended master batch, the silicone composition according to mass percent is in this silicone masterbatch: 30%-70%.
Wherein, preferred, described surface treatment ultra-fine red phosphorus is a cladded type red phosphorus, and red phosphorus content is greater than 90%.
Wherein, preferred, described lubricant is: Zinic stearas or stearic acid.
Wherein, preferred, described oxidation inhibitor be composite antioxidant Hinered phenols antioxidant and auxiliary antioxidant with 1: the mixed thing of 1-3.
Wherein, preferred, described sensitization linking agent is: Viscoat 295 TMPTA, trimethylolpropane trimethacrylate TMPTMA or cyanacrylate TAIC; Described photostabilizer is hindered amine light stabilizer and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance.
The present invention also provides a kind of making method of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product, and it comprises step:
101, masterbatch procedure of processing: above material is added tapered stirrer, below 60 degree, mix 5-10min, use then banburying mixing machine, screw pelletizer mixing under the 110-150 degree, extrude, tie rod, water-cooled, air-cooled, pelletizing, obtain radiation crosslinking thermal contraction Halogen sign shell material master batch;
102, extrusion step: described master batch is extruded under the 100-150 degree at the screw extrusion press of being furnished with a mouthful mould, plug manages to such an extent that beat extruding pipe material;
103, irradiation steps: described extruding pipe material is crosslinked at the above energy electron radiation from machine of 2.0MeV, and irradiation dose is 3.0Mrad-12.0Mrad;
104, expansion step: the tubing behind the irradiation under the 100-170 degree, vacuum expansion device expansion 2-3 doubly, cooling, typing;
105, rinse step: will expand back tubing use high pressure washing equipment wash repeatedly, air-cooled;
106, flatten step: described flushing back tubing is flattened at flaking mill obtain radiation crosslinking thermal contraction Halogen sign sleeve pipe product.
By implementing above technical scheme, have following technique effect: the prescription and the making method of cross-linking radiation thermal contraction halogen-free flameproof provided by the invention sign sleeve pipe product, the label sleeve pipe of making have performances such as good fire-retardant, mechanical, insulation, wear-resisting, anticorrosive, anti-light aging.Adopt heat to shift and print, writing is clear, and surpass 20 years work-ing life, identifies anti-wiping properties, solvent resistance is good.Easy to use, utilize nylon cable tie to be bundled in big specification cable and need the home position.Radiation crosslinking has promoted mechanical performance of products, flame retardant properties significantly.
Embodiment
Technical scheme for a better understanding of the present invention, below embodiment describe prescription provided by the invention and making method in detail.
The invention provides a kind of prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product, the ratio according to quality comprises:
Ethylene vinyl acetate copolymer (EVA) 20-40
Ethylene acrylate copolymer (EEA) 0-10
Maleic anhydride grafted polymer 1-15
Silicone master batch 1-15
Ultra-fine surface treatment active aluminium hydroxide 10-20
Ultra-fine surface treatment active hydrogen magnesium oxide 10-20
Zinc borate 1-10
Surface treatment ultra-fine red phosphorus 0-10
Organonitrogen phosphorus fire retardant 0-10
Titanium dioxide 0-5
Lubricant 0.2-1
Oxidation inhibitor 0.5-1
Sensitization linking agent 0.5-2
Photostabilizer 0.5-2
Look female 1-5.
Wherein, the propenyl acetate (EA) of the vinylacetate of described EVA (VA) or EEA amount is respectively: 5-15%, melting index 1-10.0g/10min.
Wherein, described maleic anhydride grafted polymer comprises: new LDPE (film grade) (LDPE), ethylene vinyl acetate copolymer (EVA) and polyolefin elastomer (POE), this maleic anhydride grafted polymer percentage of grafting is: 0.5-2.0%.
Wherein, described silicone master batch is: the organo-siloxane extra high molecular polymer mixes the master batch that obtains with polyolefin resin as carrier, and the silicone composition according to mass percent is in this silicone masterbatch: 30%-70%.
Wherein, described ultra-fine surface treatment active hydrogen magnesium oxide, magnesium hydroxide, surface treatment agent is silane coupling agent, titanate coupling agent or aluminate coupling agent, filler is more than or equal to 5000 orders.
Wherein, described surface treatment ultra-fine red phosphorus is a cladded type red phosphorus, and red phosphorus content is greater than 90%.
Wherein, described lubricant is: Zinic stearas or stearic acid.
Wherein, described oxidation inhibitor be the composite antioxidant Hinered phenols antioxidant [as: 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid or pentaerythritol ester] with auxiliary antioxidant [as: (two 12 carbon alcohol esters, two ten four carbon alcohols esters, two octadecanol ester, three monooctyl esters, three the last of the ten Heavenly stems ester, three (12 carbon alcohol) ester or three (16 carbon alcohol) ester] with 1: the mixed thing of 1-3.
Wherein, described sensitization linking agent is: Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA) or cyanacrylate (TAIC); Described photostabilizer is hindered amine light stabilizer [as two (2,2,6,6-tetramethyl--4-piperidines) ester or the Succinic Acid of: sebacic acid] and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance.
Embodiment one:
The EVA:20 kilogram; The EEA:2 kilogram; The polymkeric substance of low density polyethylene, ethylene vinyl acetate copolymer EVA and polyolefin elastomer POE: 10 kilograms; Silicone master batch: 2 kilograms; Ultra-fine surface treatment active aluminium hydroxide: 36 kilograms; Ultra-fine surface treatment active hydrogen magnesium oxide: 40 kilograms; Zinc borate: 2 kilograms; Surface treatment ultra-fine red phosphorus: 2 kilograms; Organonitrogen phosphorus fire retardant: 2 kilograms; Titanium dioxide: 2 kilograms; Zinic stearas: 0.4 kilogram; 2, three grades of butyl of 6--4-methylphenol and the mixture of two 12 carbon alcohol esters: 0.6 kilogram according to 1: 1; The TMPTMA:2.8 kilogram; Sebacic acid dibasic acid esters or Succinic Acid and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance: 0.6 kilogram; Look mother: 2 kilograms.
Embodiment two:
The EVA:100 kilogram; The EEA:20 kilogram; The polymkeric substance of low density polyethylene, ethylene vinyl acetate copolymer EVA and polyolefin elastomer POE: 25 kilograms; Silicone master batch: 20 kilograms; Ultra-fine surface treatment active aluminium hydroxide: 13 kilograms; Ultra-fine surface treatment active hydrogen magnesium oxide: 10 kilograms; Zinc borate: 20 kilograms; Surface treatment ultra-fine red phosphorus: 8 kilograms; Organonitrogen phosphorus fire retardant: 10 kilograms; Titanium dioxide: 3 kilograms; Stearic acid: 1.3 kilograms; 2, three grades of butyl of 6--4-methylphenol and the mixture of two 12 carbon alcohol esters: 1.4 kilograms according to 1: 1; The TMPTA:0.8 kilogram; Sebacic acid dibasic acid esters, sebacic acid dibasic acid esters or Succinic Acid and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance: 1.6 kilograms; Look mother: 5 kilograms.
Embodiment three:
The EVA:40 kilogram; The EEA:8 kilogram; The polymkeric substance of low density polyethylene, ethylene vinyl acetate copolymer EVA and polyolefin elastomer POE: 10 kilograms; Silicone master batch: 14 kilograms; Ultra-fine surface treatment active aluminium hydroxide: 18 kilograms; Ultra-fine surface treatment active hydrogen magnesium oxide: 8 kilograms; Zinc borate: 8 kilograms; Surface treatment ultra-fine red phosphorus: 6 kilograms; Organonitrogen phosphorus fire retardant: 8 kilograms; Titanium dioxide: 1 kilogram; Zinic stearas: 0.8 kilogram; 2, three grades of butyl of 6--4-methylphenol and the mixture of two 12 carbon alcohol esters: 0.8 kilogram according to 1: 1; The TAIC:0.8 kilogram; Sebacic acid dibasic acid esters or Succinic Acid and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance: 1.6 kilograms; Look mother: 4 kilograms.
The present invention also provides a kind of making method of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product, comprises step:
101, masterbatch procedure of processing: the material that the foregoing description is provided adds tapered stirrer according to above ratio, below 60 degree, mix 5-10min, use then banburying mixing machine, screw pelletizer mixing under the 110-150 degree, extrude, tie rod, water-cooled, air-cooled, pelletizing, obtain radiation crosslinking thermal contraction Halogen sign shell material master batch;
102, extrusion step: described master batch is extruded under the 100-150 degree at the screw extrusion press of being furnished with a mouthful mould, plug manages to such an extent that beat extruding pipe material;
103, irradiation steps: described extruding pipe material is crosslinked at the above energy electron radiation from machine of 2.0MeV, and irradiation dose is 3.0Mrad-12.0Mrad
104, expansion step: the tubing behind the irradiation under the 100-170 degree, vacuum expansion device expansion 2-3 doubly, cooling, typing;
105, rinse step: will expand back tubing use high pressure washing equipment wash repeatedly, air-cooled;
106, flatten step: described flushing back tubing is flattened at flaking mill obtain radiation crosslinking thermal contraction Halogen sign sleeve pipe product.
The advantage of this sign sleeve pipe product:
Halogen-free flameproof, burning does not discharge toxic and harmful, smoke density is low, meets the instruction of IEC61249 Halogen: Br, Cl content＜900ppm, Br+Cl＜1500ppm.
This sign sleeve pipe product thermal contraction, machinery, electricity, fire-retardant, corrosion-resistant, salt spray resistance, anti-solvent etc. are functional, meet UL224, ASTM D2671, American army mark SAE-AMS-DTL23053/5 standard-required.
It is good that heat shifts printing effect, and the solvent resistance of this sign sleeve pipe product meets U.S. mark MIL-STD-202F and Chinese Military Standards GJB 360A-96215 standard-required after the printing; Anti-wiping properties meets employing U.S. Military Standards SAE-81531 standard-required.
More than a kind of prescription and making method of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product was described in detail to the embodiment of the invention provides, for one of ordinary skill in the art, thought according to the embodiment of the invention, part in specific embodiments and applications all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (9)
1. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product is characterized in that the ratio according to quality comprises:
Ethylene vinyl acetate copolymer EVA 20-40
Ethylene acrylate copolymer EEA 0-10
Maleic anhydride grafted polymer 1-15
Silicone master batch 1-15
Ultra-fine surface treatment active aluminium hydroxide 10-20
Ultra-fine surface treatment active hydrogen magnesium oxide 10-20
Zinc borate 1-10
Surface treatment ultra-fine red phosphorus 0-10
Organonitrogen phosphorus fire retardant 0-10
Titanium dioxide 0-5
Lubricant 0.2-1
Oxidation inhibitor 0.5-1
Sensitization linking agent 0.5-2
Photostabilizer 0.5-2
Look female 1-5.
2. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1 is characterized in that the propenyl acetate EA content of the vinylacetate VA of described EVA or EEA is respectively: 5-15%, melting index 1-10.0g/10min.
3. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1, it is characterized in that, described maleic anhydride grafted polymer comprises: low density polyethylene, ethylene vinyl acetate copolymer EVA and polyolefin elastomer POE, this maleic anhydride grafted polymer percentage of grafting is: 0.5-2.0%.
4. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1, it is characterized in that, described silicone master batch is: organo-siloxane extra high molecular polymer and carrier blended master batch, the silicone composition according to mass percent is in this silicone masterbatch: 30%-70%.
5. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1 is characterized in that described surface treatment ultra-fine red phosphorus is a cladded type red phosphorus, and red phosphorus content is greater than 90%.
6. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1 is characterized in that described lubricant is: Zinic stearas or stearic acid.
7. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1 is characterized in that, described oxidation inhibitor be composite antioxidant Hinered phenols antioxidant and auxiliary antioxidant with 1: the mixed thing of 1-3.
8. the prescription of cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product according to claim 1, it is characterized in that described sensitization linking agent is: Viscoat 295 TMPTA, trimethylolpropane trimethacrylate TMPTMA or cyanacrylate TAIC;
Described photostabilizer is hindered amine light stabilizer and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance.
9. the making method of a cross-linking radiation thermal contraction halogen-free flameproof sign sleeve pipe product is characterized in that, comprises step:
101, masterbatch procedure of processing: above material is added tapered stirrer, below 60 degree, mix 5-10min, use then banburying mixing machine, screw pelletizer mixing under the 110-150 degree, extrude, tie rod, water-cooled, air-cooled, pelletizing, obtain radiation crosslinking thermal contraction Halogen sign shell material master batch;
102, extrusion step: described master batch is extruded under the 100-150 degree at the screw extrusion press of being furnished with a mouthful mould, plug manages to such an extent that beat extruding pipe material;
103, irradiation steps: described extruding pipe material is crosslinked at the above energy electron radiation from machine of 2.0MeV, and irradiation dose is 3.0Mrad-12.0Mrad;
104, expansion step: the tubing behind the irradiation under the 100-170 degree, vacuum expansion device expansion 2-3 doubly, cooling, typing;
105, rinse step: will expand back tubing use high pressure washing equipment wash repeatedly, air-cooled;
106, flatten step: described flushing back tubing is flattened at flaking mill obtain radiation crosslinking thermal contraction Halogen sign sleeve pipe product.
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| CN201010202572.XA CN102276905B (en) | 2010-06-13 | 2010-06-13 | A kind of formula of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product and making method |
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| CN201010202572.XA CN102276905B (en) | 2010-06-13 | 2010-06-13 | A kind of formula of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product and making method |
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| CN102276905B (en) | 2016-03-30 |
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Address after: No. 8 Longgang District of Shenzhen City, Guangdong province 518000 Longgang Street Baolong Industrial City Jinlong Avenue Patentee after: Hongshang Heat Shrinkable Materials Co., Ltd. Address before: First, 1-3 floor, Second South Industrial Park, Buji Town, Longgang District, Shenzhen District, Guangdong, Patentee before: Hongshang Heat Shrinkable Materials Co., Ltd. |
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Address after: 518000 Jinlong Avenue, Baolong Street, Longgang District, Shenzhen City, Guangdong Province Patentee after: HONGSHANG HEAT SHRINKABLE MATERIALS Co.,Ltd. Address before: No. 8 Longgang District of Shenzhen City, Guangdong province 518000 Longgang Street Baolong Industrial City Jinlong Avenue Patentee before: HONGSHANG HEAT SHRINKABLE MATERIALS Co.,Ltd. |
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