CN101615769B - Transparent double-layer heat shrinkable sheathing - Google Patents
Transparent double-layer heat shrinkable sheathing Download PDFInfo
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- CN101615769B CN101615769B CN2009100557866A CN200910055786A CN101615769B CN 101615769 B CN101615769 B CN 101615769B CN 2009100557866 A CN2009100557866 A CN 2009100557866A CN 200910055786 A CN200910055786 A CN 200910055786A CN 101615769 B CN101615769 B CN 101615769B
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Abstract
A transparent double-layer heat shrinkable sheathing comprises a sheathing inner layer and a sheathing outer layer sheathed above the sheathing inner layer; the sheathing outer layer is a crystalline modified polyolefin material layer and is prepared by the following substances by weight: 90.5-98% of thermoplastic polyolefin material, 0.5-1.5% of outer layer antioxidizer, 1-5% of lubricating and processing aid and 0.5-3% of crosslinking assistant; the sheathing inner layer is a hot melting glue layer and is prepared by the following substances by weight: 65-99% of polyamide hot melt flue and 1-35% of inner layer antioxidizer. The transparent double-layer heat shrinkable sheathing is improved in thermal ageing performance, wear-resisting property, low temperature flexibility, solvent-resistant preparation and other aspects; the transparent design of the heat shrinkable sheathing brings convenience to the monitoring of the connection condition of components from the outside of the heat shrinkable sheathing, and reduces potential safety hazard; in addition, the formula in the invention is designed by international environment-friendly standard, thus conforming to the requirement of green environment-friendly automobile advocated by the current internationalization.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly a kind of transparent double-layer heat shrinkable sheathing.
Background technology
Heat-shrinkage material is claimed polymer shape memory material again, is a kind of intelligent material of macromolecular material and radiation processing technology cross coupled.Common high molecular materials such as polyethylene, polyvinyl chloride etc. be linear structure normally; After the radiation effects of radioactive sources such as process electron accelerator becomes network structure; These materials will possess its special " memory effect ", and the material of expansion, cooling and shaping can shrink again after being heated and return to the original form.
Series of process such as the production of heat-shrinkage material need be gone through and be mixed, moulding, irradiation, expansion, gluing form.The basic principle of heat-shrinkage material is to utilize the SME of macromolecular material to process.Macromolecular materials such as polyolefin substrate give material insoluble characteristics through irradiation generation cross-linking reaction.Disappear when being warming up to its melt temperature post crystallization, this moment is with the material expansion and be cooled to below the crystalline melt point recovery of polymer crystallization attitude rapidly; Deformation " is freezed "; The material of this moment has " memory effect ", is not promptly having under other external force effects, can be retracted to original form after the heating once more.
The memory performance of heat-shrinkage material can be used for making heat-shrinkable pipe, film material and special-shaped material; Key property is that heat shrink is coated on external surface of objects; Effect such as can play insulation, protection against the tide, seal, protect and continue, the radial shrinkage ratio of shrink-down material can reach 50%-80%.Rely on the performance of these special excellences, heat-shrinkage material is widely used in key areas such as electric power, electronics, industrial and mineral facility, boats and ships, space flight and aviation, automobile.
Along with developing rapidly of China's economic, the domestic automobile manufacturing also develops by leaps and bounds, and automotive wire bundle and pipeline have been in control bigger development with heat shrinking sleeve.The quality influence of this thermal contraction casing tube is to the performance and the quality of whole automobile, and the performance of thermal contraction casing tube and quality mainly show aspects such as its insulating properties, sealing, anti-flammability, resistance to wear and oil resistant protective value.There is certain problem in the thermal contraction casing tube of prior art because the material that is adopted is aborning formed; Also there are certain defective in its performance and quality; Be difficult to satisfy of the specific (special) requirements of some special dimensions, thereby caused potential safety hazard the performance of thermal contraction casing tube.For example automobile electric wire terminal and joint are prone to wear out, and the bad generation short circuit of insulating properties causes the generation of some pyrophoricity accidents etc., thereby causes the person and the property loss of some.
In addition, because in the prior art, employed heat-shrinkable tube is opaque on the pipeline; When with this thermal contraction casing tube big envelope pipeline; Connection situation that can't be from the external observation to the internal pipeline is difficult to the monitoring to pipeline socket quality, thereby also has certain potential safety hazard.
Summary of the invention
The objective of the invention is to solve in the prior art; Thermal contraction casing tube can't satisfy the specific (special) requirements to the thermal contraction casing tube performance of specific area; And connection situation that can't be from the thermal contraction casing tube external detection to internal pipeline, thereby can't monitor the technical problems such as socket quality of thermal contraction casing tube.
In view of this; The present invention provides a kind of transparent double-layer heat shrinkable sheathing; Comprise the cover inner tube layer and be socketed on the cover outer tube layer on the inner tube layer, wherein, said cover outer tube layer is a crystal type modified polyolefine material layer; It is prepared from following material: thermoplastic olefin material 90.5-98% according to the weight meter; Outer antioxidant 0.5-1.5%; The lubricated processing aid 1-5% that reaches; Crosslinking coagent 0.5-3%; Said cover inner tube layer is a hot melt adhesive layer, and it is prepared from following material according to the weight meter: polyamide hot 65-99%; Internal layer antioxidant 1-35%.
Further, said outer antioxidant is selected from a kind of in the following material: pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester, N, N;-two (2-naphthyl) p-phenylenediamine (PPD), 2 mercapto benzimidazole, 2; 2,4-trimethyl-1,2-the second light industry bureau quinoline condensate.
Further, said lubricated and processing aid is selected from a kind of in the following material: PE wax, silicones.
Further, said crosslinking coagent is selected from a kind of in the following material: triallyl isocyanurate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate.
Further, said internal layer antioxidant is selected from a kind of in the following material: N, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester.
The transparent double-layer heat shrinkable sheathing that utilizes material manufacture provided by the invention to go out; Can satisfy the performance requirement of special dimension to thermal contraction casing tube; For example significant points such as automobile electric wire terminal, node, connector are carried out effective insulated enclosure; Can effectively prevent under the wet environment automobile electric wire terminal and joint is corroded, can carry out wear-resisting, oil resistant protection to the wire terminal joint, and because this thermal contraction casing tube is a transparent design, convenient connection situation from thermal contraction casing tube outer monitoring device in it; Guaranteed quality; Reduced potential safety hazard, the international environmental protection standard of prescription design among the present invention simultaneously meets the requirement of the environmental protection automobile that current internationalization advocates.
Embodiment
For making technical characterictic of the present invention more obviously understandable,, the present invention is done further description below in conjunction with specific embodiment.
Please refer to Fig. 1 and Fig. 2, it is respectively the perspective view and the schematic cross-section of the transparent double-layer heat shrinkable sheathing that one embodiment of the invention provides.As shown in the figure, this thermal contraction casing tube 10 comprises cover inner tube layer 12 and is socketed on the cover outer tube layer 14 on the inner tube layer 12.
Cover outer tube layer 14 is the crystal type modified polyolefine material, and it is main base material with thermoplastic olefin material, accounts for the 90.5-98% of total weight usually; Add a certain amount of outer antioxidant (accounting for the 0.5-1.5% of gross weight), lubricated processing aid (accounting for the 1-5% of gross weight), the crosslinking coagent (accounting for the 0.5-3% of gross weight) of reaching simultaneously, be prepared from through high energy gamma rays (electron accelerator or cobalt 60) cross-linking radiation.
Wherein, outer antioxidant is selected from a kind of in the following material: pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester; N, N ,-two (2-naphthyl) p-phenylenediamine (PPD), 2 mercapto benzimidazole; 2,2,4-trimethyl-1,2-the second light industry bureau quinoline condensate;
Lubricated and processing aid is selected from a kind of in the following material: PE wax, silicones;
Crosslinking coagent is selected from a kind of in the following material: triallyl isocyanurate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate.
Cover inner tube layer 12 is a hot melt adhesive layer, is main base material with polyamide hot, accounts for the 65-99% of total weight usually; Adding a certain amount of internal layer antioxidant (accounting for gross weight 1-35%) is prepared from.Its preparation process comprises: choose raw material; Through the double screw extruder granulation; The material grain that oven dry is made; , with the extruder extrusion molding of the material grain of making through special head.
Wherein, internal layer antioxidant is selected from a kind of in the following material: N, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester.
The double-layer heat shrinkable sheathing of producing according to above prescription can effectively prevent copper corrosion and thermo-oxidative ageing, can in rainwater and wet environment, carry out sealed insulation to automotive wire bundle contact and terminal.And the double-layer heat shrinkable sheathing according to above prescription is produced is transparent; Convenient situation from the connection of device in it of thermal contraction casing tube outer monitoring; When especially being applied to the field machining use of multiply wire harness insulated enclosure or special-shaped Wiring harness terminal and connector; Whether can clearly judge product by effective protection, whether judgement that simultaneously can be clear and intuitive when the inspection fault is protected node, terminal to leak, and whether the glue of internal layer has loss.The quality that this has just guaranteed its application product has greatly reduced potential safety hazard.
Embodiment one
At first heat-obtaining plasticity polyolefine material is 90.5 kilograms; 1.5 kilograms of pentaerythritol esters; 5 kilograms in PE wax; 3 kilograms of triallyl isocyanurates mix the crystal type modified polyolefine material through high energy gamma rays (electron accelerator or cobalt 60) cross-linking radiation.
Next gets 65 kilograms of polyamide hots; N, 35 kilograms of N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazines are mixed into hot melt adhesive layer.
Then above-mentioned crystal type modified polyolefine material is placed skin, hot melt adhesive layer places internal layer, through special installation fusion coextrusion mold, forms bilayer sleeve.
At last bilayer sleeve is finalized the design through expansion, promptly obtain a kind of transparent double-layer heat shrinkable sheathing of the present invention.
Embodiment two
At first heat-obtaining plasticity polyolefine material is 95 kilograms; 1 kilogram of dilauryl thiodipropionate; 1 kilogram of silicones; 3 kilograms of trimethylolpropane triacrylate are mixed the crystal type modified polyolefine material through high energy gamma rays (electron accelerator or cobalt 60) cross-linking radiation.
Next gets 80 kilograms of polyamide hots; 20 kilograms of pentaerythritol esters are mixed into hot melt adhesive layer.
Then above-mentioned crystal type modified polyolefine material is placed skin, hot melt adhesive layer places internal layer, through special installation fusion coextrusion mold, forms bilayer sleeve.
At last bilayer sleeve is finalized the design through expansion, promptly obtain a kind of transparent double-layer heat shrinkable sheathing of the present invention.
Embodiment three
At first heat-obtaining plasticity polyolefine material is 98 kilograms; N, N, 0.5 kilogram of-two (2-naphthyl) p-phenylenediamine (PPD); 1 kilogram of silicones; 0.5 kilogram of trimethylol-propane trimethacrylate mixes the crystal type modified polyolefine material through high energy gamma rays (electron accelerator or cobalt 60) cross-linking radiation.
Next gets 99 kilograms of polyamide hots; 1 kilogram of dilauryl thiodipropionate is mixed into hot melt adhesive layer.
Then above-mentioned crystal type modified polyolefine material is placed skin, hot melt adhesive layer places internal layer, through special installation fusion coextrusion mold, forms bilayer sleeve.
At last bilayer sleeve is finalized the design through expansion, promptly obtain a kind of transparent double-layer heat shrinkable sheathing of the present invention
Please referring to table 1, it has provided the performance test table of using the made product (for example, thermal contraction casing tube) of heat-shrinkage material that above embodiment provides.
From table 1, can find out; The heat-shrinkage material that above embodiment provided has higher serviceability; Adopt the thermal contraction casing tube of this heat-shrinkage material preparation; Have very big raising at aspects such as heat aging performance, anti-wear performance, low temperature flexibility and solvent-resistings, the sleeve pipe as nonmetal pipelines such as motor vehicles can effectively prevent the mutual abrasion that close pipeline takes place in motion process.This prescription design simultaneously meets international environmental protection standard, meets the requirement of the environmental protection automobile that current internationalization advocates.
More than being merely for example, is not that protection scope of the present invention should be as the criterion with the scope that claims are contained in order to qualification the present invention.
Table 1
Claims (5)
1. a transparent double-layer heat shrinkable sheathing comprises the cover inner tube layer and is socketed on the cover outer tube layer on the inner tube layer, it is characterized in that:
Said cover outer tube layer is a crystal type modified polyolefine material layer, and it is prepared from following material according to the weight meter:
Thermoplastic olefin material 90.5-98%;
Outer antioxidant 0.5-1.5%;
The lubricated processing aid 1-5% that reaches;
Crosslinking coagent 0.5-3%;
Said cover inner tube layer is a hot melt adhesive layer, and it is prepared from following material according to the weight meter:
Polyamide hot 65-99%;
Internal layer antioxidant 1-35%.
2. transparent double-layer heat shrinkable sheathing according to claim 1; It is characterized in that said outer antioxidant is selected from a kind of in the following material: pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester, N, N;-two (2-naphthyl) p-phenylenediamine (PPD), 2 mercapto benzimidazole, 2; 2,4-trimethyl-1,2-the second light industry bureau quinoline condensate.
3. transparent double-layer heat shrinkable sheathing according to claim 1 is characterized in that, said lubricated and processing aid is selected from a kind of in the following material: PE wax, silicones.
4. transparent double-layer heat shrinkable sheathing according to claim 1 is characterized in that, said crosslinking coagent is selected from a kind of in the following material: triallyl isocyanurate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate.
5. transparent double-layer heat shrinkable sheathing according to claim 1; It is characterized in that; Said internal layer antioxidant is selected from a kind of in the following material: N; N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, pentaerythritol ester, dilauryl thiodipropionate, thio-2 acid octadecyl ester.
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| CN2009100557866A CN101615769B (en) | 2009-07-31 | 2009-07-31 | Transparent double-layer heat shrinkable sheathing |
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| CN101615769B true CN101615769B (en) | 2012-03-28 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532643B (en) * | 2010-12-16 | 2016-02-03 | 深圳市宏商材料科技股份有限公司 | A kind of formula of oil-resisting type thermal contraction bilayer sleeve and complete processing thereof |
| CN102161791A (en) * | 2011-01-21 | 2011-08-24 | 上海长园电子材料有限公司 | Colored thermal shrinkage material and sleeve |
| CN103183858A (en) * | 2011-12-29 | 2013-07-03 | 深圳市宏商材料科技股份有限公司 | Oil resistant type semihard flame retardation thermal contraction double layer sleeving and processing technology |
| CN102993711A (en) * | 2012-08-17 | 2013-03-27 | 安徽凯迪电气有限公司 | Automobile nylon rivet and manufacture method thereof |
| CN106221600A (en) * | 2016-08-17 | 2016-12-14 | 安徽兴源塑料包装有限公司 | A kind of thermal contraction gum cover |
| CN108948497A (en) * | 2018-07-27 | 2018-12-07 | 上海长园电子材料有限公司 | A kind of transparent flame-retarding double-wall heat shrinkage casing and preparation method thereof |
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| CN2437951Y (en) * | 2000-06-23 | 2001-07-04 | 樊邦弘 | Rubber line lamp string |
| CN1327908A (en) * | 2001-07-05 | 2001-12-26 | 卢沛女 | Method for manufacturing thermally shrinking dual-layer sleeved tube |
| WO2002019494A1 (en) * | 2000-08-30 | 2002-03-07 | Chunma Corporation | Armature for heat shrinkable sleeve and heat shrinkable sleeve comprising it |
| CN2646922Y (en) * | 2003-07-15 | 2004-10-06 | 李馨春 | Thermal shrinkable casing pipe for cable splice |
| CN101404396A (en) * | 2008-04-24 | 2009-04-08 | 上海长园电子材料有限公司 | Double-layer thermal contraction casing tube |
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Patent Citations (5)
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| CN2437951Y (en) * | 2000-06-23 | 2001-07-04 | 樊邦弘 | Rubber line lamp string |
| WO2002019494A1 (en) * | 2000-08-30 | 2002-03-07 | Chunma Corporation | Armature for heat shrinkable sleeve and heat shrinkable sleeve comprising it |
| CN1327908A (en) * | 2001-07-05 | 2001-12-26 | 卢沛女 | Method for manufacturing thermally shrinking dual-layer sleeved tube |
| CN2646922Y (en) * | 2003-07-15 | 2004-10-06 | 李馨春 | Thermal shrinkable casing pipe for cable splice |
| CN101404396A (en) * | 2008-04-24 | 2009-04-08 | 上海长园电子材料有限公司 | Double-layer thermal contraction casing tube |
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