CN1760997A - Environmental protection type fire retardant thermal shrinkage tube without halogen - Google Patents

Environmental protection type fire retardant thermal shrinkage tube without halogen Download PDF

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Publication number
CN1760997A
CN1760997A CN 200510036926 CN200510036926A CN1760997A CN 1760997 A CN1760997 A CN 1760997A CN 200510036926 CN200510036926 CN 200510036926 CN 200510036926 A CN200510036926 A CN 200510036926A CN 1760997 A CN1760997 A CN 1760997A
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halogen
thermal shrinkage
environmental protection
fire retardant
protection type
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CN 200510036926
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CN100354989C (en
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赵成刚
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ChangYuan Group Ltd.
Sanlian Thermal Contrative Materials Co., Ltd., Dongguan
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赵成刚
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Abstract

Through milling granulating copolymers of ethylene - vinyl acetate, silicon rubber, red phosphorus in microcapsule, fire retardant in phosphor nitrogen family, inorganic retardant, lubricant, antioxidant, color batch, light stabilizer, the thermal shrinkage tube is fabricated after procedure of extrusion molding, radiation cross linking, and expansion forming. Raw material in low cost for the tube is easy to be obtained. Performance reaches to requirement of USA UL224 standard. Features are: simple preparation method and being suitable to industrialization. In procedures of production, storage and use, the thermal shrinkage tube does not pollute environment and is not harmful to human body. The product is accorded with requirement of ROHS instruction of EU as a product of green environmental protection.

Description

A kind of environmental protection type fire retardant thermal shrinkage tube without halogen
[technical field]
The present invention relates to the fire retardant thermal shrinkage tube field, especially a kind of environmental protection type fire retardant thermal shrinkage tube without halogen.
[technical background]
Present commercially available fire retardant thermal shrinkage tube contains lead (Pb), cadmium (Cd), mercury (Hg), Cr VI (Cr+6), Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers (PBDE).Hazardous substance illegal instruction in European Union's electronic motor equipment (being called for short ROHS instructs) is implemented in beginning on July 1st, 2006 is formal, clearly stipulates in the ROHS instruction: ban use of lead (Pb), cadmium (Cd), mercury (Hg), Cr VI (Cr+6), Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers (PBDE) in the products such as electronic motor.Fire retardant thermal shrinkage tube if can not reach the ROHS of European Union command request, will directly influence products exports such as electronic motor as one of common components in the products such as electronic motor.Therefore market presses for the fire retardant thermal shrinkage tube that meets the ROHS of European Union command request.
[summary of the invention]
The purpose of this invention is to provide a kind of environmental protection type fire retardant thermal shrinkage tube without halogen, this heat-shrink tube can meet the ROHS of European Union command request.
Another object of the present invention provides the purposes that a kind of environmental protection type fire retardant thermal shrinkage tube without halogen material is formed.
The object of the present invention is achieved like this: this a kind of environmental protection type fire retardant thermal shrinkage tube without halogen, it is made up of following material according to the weight meter: ethylene-vinyl acetate copolymer 100, silicon rubber 3-30, microcapsule red phosphorus 3-20, phosphorus-nitrogen containing flame retardant 5-40, inorganic combustion inhibitor 10-80, lubricant 0.4-2.5, antioxidant 0.4-1.5, color masterbatch 3-15, light stabilizer 0.5-4.Above-mentioned substance is all commercially available.
The melt index MI=1.5-8g/min of described ethylene-vinyl acetate copolymer, vinyl acetate content=12--30%.
Described silicon rubber is silicon rubber gross rubber, does not contain metallic lead, cadmium, mercury and Cr VI.
The granularity of described microcapsule red phosphorus must and not contain metallic lead, cadmium, mercury and Cr VI greater than 300 orders.
Described phosphorus-nitrogen containing flame retardant is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: melamine, melamine cyanurate, melamine phosphoric acid fat, polyphosphoric acid amine.
Described inorganic combustion inhibitor is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: aluminium hydroxide, magnesium hydroxide, Firebrake ZB.
Described lubricant is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: stearic acid, zinc stearate, calcium stearate, Ployethylene Wax.
Described color masterbatch does not contain metallic lead, cadmium, mercury and Cr VI.
The preparation method of environmental protection type fire retardant thermal shrinkage tube without halogen of the present invention, be with above-mentioned ethylene-vinyl acetate copolymer 100 according to the weight meter, silicon rubber 3-30, microcapsule red phosphorus 3-20, phosphorus-nitrogen containing flame retardant 5-40, inorganic combustion inhibitor 10-80, lubricant 0.4-1.5, antioxidant 0.4-1.5, color masterbatch 3-15, light stabilizer 0.5-4 fully mixes the parallel double-screw extruder mixing granulator through high-speed mixer, single screw extrusion machine is extruded into tubing, described tubing is through cobalt 60 or electron accelerator 50-180KGY crosslinking with radiation, and the tubing behind the crosslinking with radiation is expanded 2-5 doubly under 90--150 ℃ of temperature, obtain environmental protection type fire retardant thermal shrinkage tube without halogen.
The material of environmental protection type fire retardant thermal shrinkage tube without halogen of the present invention is formed, and can be used for preparing other environment-friendly halogen-free flame-proof pyrocondensation devices except that environmental protection type fire retardant thermal shrinkage tube without halogen.
The invention has the beneficial effects as follows: Zhi Bei fire retardant thermal shrinkage tube without halogen according to the method described above, raw material are easy to get, and are cheap, are suitable for industrialization production, and performance index meet U.S. UL224 standard-required fully.Main performance index is as follows: tensile strength 〉=10.4Mpa; Elongation at break 〉=200%; Under 158 ℃ of conditions, 168 hours aging after, tensile strength 〉=7.28Mpa, elongation at break 〉=100%; Dielectric voltage withstand: 2500V 60S passes through; Specific insulation 〉=1*10 14Ohmcm; Copper corrosion: under 158 ℃ of conditions, not blackening of copper cash in 168 hours; Anti-flammability: meet VW-1.This fire retardant thermal shrinkage tube without halogen, in production, storage, use, environmentally safe, harmless, can not produce pernicious gas during burning, meet the ROHS of European Union command request fully, after on July 1st, 2006, the ROHS of European Union instruction was implemented, for products export European Union such as electronic motors, on these parts of heat-shrink tube, provide assurance.Concrete environmental index is as follows: plumbous (Pb)＜2ppm, cadmium (Cd)＜2ppm, mercury (Hg)＜2ppm, Cr VI (Cr+6)＜2ppm, Polybrominated biphenyl (PBB)＜2ppm and Poly Brominated Diphenyl Ethers (PBDE)＜2ppm.
[embodiment]
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
Get ethylene-vinyl acetate copolymer 100Kg, silicon rubber 5Kg, microcapsule red phosphorus 10Kg, melamine cyanurate 30Kg, aluminium hydroxide 30Kg, Firebrake ZB 10Kg, stearic acid 1Kg, antioxidant 1Kg, color masterbatch 5Kg, light stabilizer 0.8Kg.Above-mentioned substance is fully mixed through high-speed mixer, the parallel double-screw extruder mixing granulator, single screw extrusion machine is extruded into tubing, electron accelerator 100KGY crosslinking with radiation, tubing behind the crosslinking with radiation is expanded 2 times under 90--150 ℃ of temperature, obtain environmental protection type fire retardant thermal shrinkage tube without halogen.
Embodiment 2
Get ethylene-vinyl acetate copolymer 100Kg, silicon rubber 3Kg, microcapsule red phosphorus 15Kg, polyphosphoric acid amine 25Kg, aluminium hydroxide 15Kg, magnesium hydroxide 10Kg, Firebrake ZB 5Kg, stearic acid 0.6Kg, Ployethylene Wax 1.5Kg, antioxidant 1.1Kg, color masterbatch 5Kg, light stabilizer 0.9Kg.Above-mentioned substance is fully mixed through high-speed mixer, the parallel double-screw extruder mixing granulator, single screw extrusion machine is extruded into tubing, electron accelerator 120KGY crosslinking with radiation, tubing behind the crosslinking with radiation is expanded 2 times under 90--150 ℃ of temperature, obtain environmental protection type fire retardant thermal shrinkage tube without halogen.
This heat-shrink tube in production, storage, use, environmentally safe, harmless, can not produce pernicious gas during burning, meet the ROHS of European Union command request fully, be a kind of Green Product.

Claims (10)

1. environmental protection type fire retardant thermal shrinkage tube without halogen, it is characterized in that: described it form by following material according to the weight meter: ethylene-vinyl acetate copolymer 100, silicon rubber 3-30, microcapsule red phosphorus 3-20, phosphorus-nitrogen containing flame retardant 5-40, inorganic combustion inhibitor 10-80, lubricant 0.4-2.5, antioxidant 0.4-1.5, color masterbatch 3-15, light stabilizer 0.5-4.
2. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1 is characterized in that: the melt index MI=1.5-8g/min of described ethylene-vinyl acetate copolymer, vinyl acetate content=12--30%.
3. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1, it is characterized in that: described silicon rubber is silicon rubber gross rubber, does not contain metallic lead, cadmium, mercury and Cr VI.
4. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1, it is characterized in that: the granularity of described microcapsule red phosphorus must and not contain metallic lead, cadmium, mercury and Cr VI greater than 300 orders.
5. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1 is characterized in that: described phosphorus-nitrogen containing flame retardant is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: melamine, melamine cyanurate, melamine phosphoric acid fat, polyphosphoric acid amine.
6. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1 is characterized in that: described inorganic combustion inhibitor is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: aluminium hydroxide, magnesium hydroxide, Firebrake ZB.
7. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1 is characterized in that: described lubricant is following a kind of material or more than one materials and does not all contain metallic lead, cadmium, mercury and Cr VI: stearic acid, zinc stearate, calcium stearate, Ployethylene Wax.
8. the described a kind of environmental protection type fire retardant thermal shrinkage tube without halogen of claim 1, it is characterized in that: described color masterbatch does not contain metallic lead, cadmium, mercury and Cr VI.
9. the preparation method of an environmental protection type fire retardant thermal shrinkage tube without halogen as claimed in claim 1, it is characterized in that: with described ethylene-vinyl acetate copolymer 100 according to the weight meter, silicon rubber 3-30, microcapsule red phosphorus 3-20, phosphorus-nitrogen containing flame retardant 5-40, inorganic combustion inhibitor 10-80, lubricant 0.4-1.5, antioxidant 0.4-1.5, color masterbatch 3-15, light stabilizer 0.5-4 fully mixes the parallel double-screw extruder mixing granulator through high-speed mixer, single screw extrusion machine is extruded into tubing, described tubing is through cobalt 60 or electron accelerator 50-180KGY crosslinking with radiation, and the tubing behind the crosslinking with radiation is expanded 2-5 doubly under 90--150 ℃ of temperature, obtain environmental protection type fire retardant thermal shrinkage tube without halogen.
10. the purposes of the material of an environmental protection type fire retardant thermal shrinkage tube without halogen as claimed in claim 1 composition is characterized in that: be used to prepare other environment-friendly halogen-free flame-proof pyrocondensation devices except that environmental protection type fire retardant thermal shrinkage tube without halogen.
CNB2005100369267A 2005-09-01 2005-09-01 Environmental protection type fire retardant thermal shrinkage tube without halogen Active CN100354989C (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387646C (en) * 2006-05-30 2008-05-14 广州凯恒科塑有限公司 Fire-retarding thermal-shrinked indicated double pipe of radiant cross-linked and its preparation
CN101993589A (en) * 2009-08-13 2011-03-30 深圳市沃尔核材股份有限公司 Silicon rubber shrinkable tube and preparation method thereof
CN102093626A (en) * 2010-12-20 2011-06-15 安徽中鼎密封件股份有限公司 Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof
CN101956876B (en) * 2009-07-20 2013-08-21 深圳市沃尔核材股份有限公司 Fluoroelastomer heat-shrinkable tube and manufacturing method thereof
CN103617829A (en) * 2013-12-03 2014-03-05 国家电网公司 Temperature memory color-changing insulating material and insulating bush
CN103694551A (en) * 2013-12-21 2014-04-02 深圳市沃尔核材股份有限公司 Irradiation crosslinking environment-friendly fire-retardant material for non-foaming pipe wall in heat shrinkage and application thereof
CN106221112A (en) * 2016-08-18 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of modified silicon rubber heat-shrink tube and preparation method thereof
CN106221207A (en) * 2016-08-18 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of polyethylene/nylon heat-shrink tube and preparation method thereof
CN106217917A (en) * 2016-08-25 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of Making method of environment-friendlyflame flame retardant polyolefin hot pyrocondensation pipe
CN106280492A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of fire retardant thermal shrinkage tube of resistance to diesel oil and preparation method thereof
CN106279950A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of modified bus-bar shrinkable tube and preparation method thereof
CN106279948A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of environmental protection type fire retardant thermal shrinkage tube without halogen
CN106279951A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof
CN106496734A (en) * 2016-10-21 2017-03-15 扬州大学 The production method of polyolefin heat-shrink tube is pressed in a kind of environmental-protection flame-retardant
CN108129734A (en) * 2018-01-08 2018-06-08 长园电子（东莞）有限公司 A kind of combustion gas protection of pipe fire retardant thermal shrinkage tube through walls and preparation method thereof
CN112280160A (en) * 2020-10-13 2021-01-29 深圳市沃尔热缩有限公司 Irradiation crosslinking thermal shrinkage material and preparation method thereof

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CN1091296C (en) * 1999-12-24 2002-09-18 中国科学院上海原子核研究所 Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting
CN1137932C (en) * 2000-04-07 2004-02-11 中国科学院上海原子核研究所 Low-temp thermoshrinking halogen-free polyolefine material with properties of radiation cross-linking, low smoke and flame retardation
JP2001347566A (en) * 2000-06-06 2001-12-18 Tokin Corp Heat-shrinkable tube, heat-shrinkable sheet and method for shrinkage thereof
CN1294962A (en) * 2000-08-22 2001-05-16 张义刚 Manufacture of thermally shrinking pipe
CN1152919C (en) * 2001-12-29 2004-06-09 中国科学院长春应用化学研究所 Prepn of thermally shrinking pipe using trans-polyisoprene blend
CN1294235C (en) * 2004-11-09 2007-01-10 四川大学 Melamine cyanuric acid red phosphorous-based microcapsule and its preparation method and use

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387646C (en) * 2006-05-30 2008-05-14 广州凯恒科塑有限公司 Fire-retarding thermal-shrinked indicated double pipe of radiant cross-linked and its preparation
CN101956876B (en) * 2009-07-20 2013-08-21 深圳市沃尔核材股份有限公司 Fluoroelastomer heat-shrinkable tube and manufacturing method thereof
CN101993589A (en) * 2009-08-13 2011-03-30 深圳市沃尔核材股份有限公司 Silicon rubber shrinkable tube and preparation method thereof
CN101993589B (en) * 2009-08-13 2014-10-22 深圳市沃尔核材股份有限公司 Silicon rubber shrinkable tube and preparation method thereof
CN102093626A (en) * 2010-12-20 2011-06-15 安徽中鼎密封件股份有限公司 Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof
CN103617829A (en) * 2013-12-03 2014-03-05 国家电网公司 Temperature memory color-changing insulating material and insulating bush
CN103694551A (en) * 2013-12-21 2014-04-02 深圳市沃尔核材股份有限公司 Irradiation crosslinking environment-friendly fire-retardant material for non-foaming pipe wall in heat shrinkage and application thereof
CN106221207A (en) * 2016-08-18 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of polyethylene/nylon heat-shrink tube and preparation method thereof
CN106221112A (en) * 2016-08-18 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of modified silicon rubber heat-shrink tube and preparation method thereof
CN106280492A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of fire retardant thermal shrinkage tube of resistance to diesel oil and preparation method thereof
CN106279950A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of modified bus-bar shrinkable tube and preparation method thereof
CN106279948A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of environmental protection type fire retardant thermal shrinkage tube without halogen
CN106279951A (en) * 2016-08-18 2017-01-04 苏州泰斯拓伟机电设备有限公司 A kind of halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof
CN106217917A (en) * 2016-08-25 2016-12-14 苏州泰斯拓伟机电设备有限公司 A kind of Making method of environment-friendlyflame flame retardant polyolefin hot pyrocondensation pipe
CN106496734A (en) * 2016-10-21 2017-03-15 扬州大学 The production method of polyolefin heat-shrink tube is pressed in a kind of environmental-protection flame-retardant
CN108129734A (en) * 2018-01-08 2018-06-08 长园电子（东莞）有限公司 A kind of combustion gas protection of pipe fire retardant thermal shrinkage tube through walls and preparation method thereof
CN112280160A (en) * 2020-10-13 2021-01-29 深圳市沃尔热缩有限公司 Irradiation crosslinking thermal shrinkage material and preparation method thereof

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