CN102709007B - Thermal setted coextruded heat shrinkable sleeving and method for producing same - Google Patents
Thermal setted coextruded heat shrinkable sleeving and method for producing same Download PDFInfo
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- CN102709007B CN102709007B CN201210239715.3A CN201210239715A CN102709007B CN 102709007 B CN102709007 B CN 102709007B CN 201210239715 A CN201210239715 A CN 201210239715A CN 102709007 B CN102709007 B CN 102709007B
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Abstract
A thermal setted coextruded heat shrinkable sleeving comprises a reaction type hot melting adhesive inner layer (10), wherein an outer layer is a thermal shrinkage layer (20) which takes thermoplastics type polyolefin as a main material. The reaction type hot melting adhesive inner layer and the thermal shrinkage outer layer are coextruded into a composite sleeving, a high-energy electron accelerator is used to irradiate the sleeving, only the material of the outer layer is controlled for cross bonding, and the material of the inner layer is not cross bonded. The thermal setted coextruded heat shrinkable sleeving in the invention can completely substitute a common hotmelt double-walled heat-shrinkable sleeving under high temperature, high humidity, acid, alkali and other special working environments, so the insulation, sealing, moistureproof and shockproof effects are improved, moreover, the special materials of the inner layer and the outer layer belong to environmental protection materials, and the harmful substances and heavy metal control provisions of the Restriction of the use of Certain Hazardous Substances in Electrical and Electronic Equipment (ROSH) of the European union are satisfied.
Description
Technical field
The present invention relates to insulating material, particularly for the insulating material of electric connection place insulated enclosure.
Background technology
At present, have no the research and development report of thermosetting composite type heat Heat-Shrinkable Tubings both at home and abroad, although there is heat curing-type PUR product on market, as: reaction type polyurethane hot-melt adhesive, response type epoxy resin PUR etc., but exist and be wrapped by object and raise and cause that seal failure, insulation decline, vibration comes off and the safe mass problem such as reliability reduction with ambient temperature, use and cannot refer in the special producing technique of thermal shrinkage type double wall casing, its application has significant limitation.
Summary of the invention
The present invention, for solving the problems of the technologies described above, adopts PUR internal layer to add thermoplastics type's outer layer of polyethene by the mode of coextrusion mold, and a kind of heat curing-type compound thermal shrink sleeve and preparation method thereof is provided.
Thermal contraction casing tube of the present invention comprises the reaction type hot-fusible glue-line of internal layer, and skin is that major ingredient is the polyolefinic shrink wrap layer of thermoplastics type.Described major ingredient be thermoplastics type's polyolefin shrink wrap layer component by volume proportioning be: polyethylene is 55～80 parts; Material modified is 15～30 parts; 5～15 parts of auxiliary agents, described polyethylene is low density polyethylene (LDPE) or medium density polyethylene.
Further improvement of the present invention is: described 15～30 parts of material modified components by volume allocation proportion are 5～10 parts of ethylene propylene diene rubbers, 10～20 parts of polyolefin elastomers, wherein the index of polyolefin elastomer is: melt index is that 1.5～5.0, VA content is 14～28%.
Further improvement more of the present invention is: described auxiliary agent is carbon black, fire retardant, sensitizer, lubricant and antioxidant, and described 5～15 parts of adjuvant components concrete proportioning is by volume that carbon black is 1～3 part; Fire retardant is 1～5 part, aluminium hydroxide; Sensitizer is 1～2 part; Lubricant is 1～2 part; Antioxidant is 1～3 part.
Further improvement of the present invention is: the component of described reaction type hot-fusible glue internal layer by volume proportioning is: 50～70 parts of polyolefin elastomers, 5～10 parts of flexibilizer, 22～30 parts of tackifying resins, 1～5 part, antioxidant, 1～3 part of polymerization inhibitor, 1～2 part of thermal initiator.
The manufacture method of above-mentioned heat curing-type compound thermal shrink sleeve comprises the following steps: A. is that the polyolefinic outer coextrusion mold of thermoplastics type is composite bushing by the internal layer of reaction type hot-fusible glue and major ingredient, described internal layer thickness is 0.5～1.5mm, and extrusion temperature is 70～130 ℃; Outer layer thickness is 1～5mm, and extrusion temperature is 90～150 ℃; B. by high-energy electron accelerator, this sleeve pipe is carried out to irradiation, the parameter of described high-energy electron accelerator is 3.0Mev, 30mA, irradiation dose is 4～12Mrad, irradiation speed is 1～150m/min according to ectonexine thickness sum and product diameter adjusting range, and the control of irradiation described in step B is for only cladding material is crosslinked; C. by heating, internal diameter is expanded, adopted heating pressurization expanded inner diameter, heating-up temperature is 120～150 ℃, and pressure control is 0.1MPa～0.7MPa, and 2～5 times for original diameter are controlled in internal diameter expansion.
Also have a kind of manufacture method of heat curing-type compound thermal shrink sleeve to comprise the following steps: A '. reaction type hot-fusible glue internal layer is coated in to major ingredient on the outer field inwall of thermoplastics type's polyolefin, forms composite bushing; B '. by high-energy electron accelerator, this inner layer material and cladding material are carried out to irradiation, control is only crosslinked for cladding material, and inner layer material is crosslinked; C '. by heating, internal diameter is expanded.
Thermosetting composite type heat Heat-Shrinkable Tubings in the present invention not only can substitute insulation, sealing, protection against the tide, the antihunt action of common heat molten type double wall heat Heat-Shrinkable Tubings in-30～80 ℃ of scopes of application, and at particular job environment such as high temperature (within the scope of 80～120 ℃), high humidity (humidity is greater than 95%), acid (PH3～5) and alkali (PH8～12), can also cannot not reach softeningly, flow, adeciduate requirement, be wrapped by object (motor, element and cable) surface, playing the effect of insulated enclosure, moistureproof protection.Improve greatly and be wrapped by object (motor, element and cable wire harness), long-term reliability of operation and fail safe in the adverse circumstances such as high temperature, high humidity, soda acid." heat curing-type PUR " in thermosetting composite type heat Heat-Shrinkable Tubings and " thermoplastics type's thermal contraction proprietary material ", belong to environment-friendly materials, meet the regulation of the ROSH of European Union harmful substance and heavy metal control.
Accompanying drawing explanation
Fig. 1 is heat curing-type compound thermal shrink sleeve cross-sectional schematic of the present invention.
Embodiment
In conjunction with above-mentioned accompanying drawing explanation specific embodiments of the invention.
In Fig. 1, this heat curing-type compound thermal shrink sleeve comprises the reaction type hot-fusible glue-line 10 of internal layer, skin is that major ingredient is the polyolefinic shrink wrap layer 20 of thermoplastics type, described major ingredient be thermoplastics type's polyolefin shrink wrap layer 20 component by volume proportioning be: low-density or medium density polyethylene are 55～80 parts; Material modified is 15～30 parts; 5～15 parts of auxiliary agents.
Wherein 15～30 parts of material modified components by volume allocation proportion be 5～10 parts of ethylene propylene diene rubbers, 10～20 parts of polyolefin elastomers, the index of polyolefin elastomer is: melt index is 1.5～5.0, VA(vinyl acetate) content 14～28%.
Described auxiliary agent is carbon black, fire retardant, sensitizer, lubricant and antioxidant, wherein the component of 5～15 parts of auxiliary agents by volume concrete proportioning be that carbon black is 1～3 part; Fire retardant is 1～5 part, aluminium hydroxide; Sensitizer is 1～2 part; Lubricant is 1～2 part; Antioxidant is 1～3 part.
The component of described reaction type hot-fusible glue-line 10 by volume proportioning is: 50～70 parts of polyolefin elastomers, 5～10 parts of flexibilizer, 22～30 parts of tackifying resins, 1～5 part, antioxidant, 1～3 part of polymerization inhibitor, 1～2 part of thermal initiator.
The manufacture method of this heat curing-type compound thermal shrink sleeve comprises the following steps: A. is that the polyolefinic outer coextrusion mold of thermoplastics type is composite bushing by the internal layer of reaction type hot-fusible glue and major ingredient, described internal layer thickness is 0.5～1.5mm, and extrusion temperature is 70～130 ℃; Outer layer thickness is 1～5mm, and extrusion temperature is 90～150 ℃; B. by high-energy electron accelerator, this sleeve pipe is carried out to irradiation, the parameter of described high-energy electron accelerator is 3.0Mev, 30mA, irradiation dose is 4～12Mrad, irradiation speed is 1～150m/min according to ectonexine thickness sum and product diameter adjusting range, and the control of irradiation described in step B is for only cladding material is crosslinked; C. by heating, internal diameter is expanded, internal diameter expansion scope is original diameter 2～5 times.
Also have a kind of manufacture method of heat curing-type compound thermal shrink sleeve to comprise the following steps: A '. reaction type hot-fusible glue internal layer is coated in to major ingredient on the outer field inwall of thermoplastics type's polyolefin, forms composite bushing; B '. by high-energy electron accelerator, this inner layer material and cladding material are carried out to irradiation, control is only crosslinked for cladding material, and inner layer material is crosslinked; C '. by heating, internal diameter is expanded.
The present invention is by internal layer hot melt curing reaction type PUR and two kinds of special materials of outer thermal contraction proprietary material, be shaped to the semi-finished product of thermosetting composite double layer thermal contraction casing tube in two extruders coextru-lamination, this semi-finished product, be under 90～130 ℃ of conditions in the temperature of co-extrusion, crosslinked and not curing in its internal layer reaction type hot-fusible glue and outer wall composite molding process, use the high-energy electron accelerator of 2.5～5.0Mev, irradiation dose is controlled under the radiation parameter of 4～12Mrad scope, do not occur under crosslinked and curing prerequisite at internal layer thermosetting reaction type hot-fusible glue, controlling cladding material produces crosslinked.Semi-finished product after irradiation are heated to be forced in 120～150 ℃, pipe in the production process of thermosetting compound thermal shrink sleeve finished product that is expanded to 2～5 times under 0.1MPa～0.7MPa pressure in airtight expansion device, control reaction type hot-fusible glue crosslinked and not curing, thermosetting compound thermal shrink sleeve finished product after this expansion is in application of heat process, it is crosslinked that its reaction type hot-fusible glue of (can setting crosslinking curing temperature/time according to client's actual demand) in the time that its heating-up temperature is greater than 200 ℃ occurs, and gets final product solidifying and setting after cooling.
Heat curing-type compound thermal shrink sleeve of the present invention has solved in actual applications and has been wrapped by object and raises and cause seal failure with ambient temperature, and insulation declines, vibration comes off, the safe mass problems such as reliability reduction.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (8)
1. a heat curing-type compound thermal shrink sleeve, is characterized in that: this thermal contraction casing tube comprises the reaction type hot-fusible glue-line (10) of internal layer, and skin is that major ingredient is the polyolefinic shrink wrap layer of thermoplastics type (20); The component that described major ingredient is thermoplastics type's polyolefin shrink wrap layer (20) by volume proportioning is: low-density or medium density polyethylene are 55 parts; Containing the material modified of ethylene propylene diene rubber and polyolefin elastomer is 30 parts; 15 parts of auxiliary agents, described auxiliary agent is carbon black, fire retardant, sensitizer, lubricant and antioxidant.
2. heat curing-type compound thermal shrink sleeve according to claim 1, is characterized in that: described 30 parts of material modified components by volume allocation proportion are 10 parts of ethylene propylene diene rubbers, 20 parts of polyolefin elastomers.
3. heat curing-type compound thermal shrink sleeve according to claim 2, is characterized in that: the index of described polyolefin elastomer is: melt index is 1.5～5.0, VA content 14～28%, wherein VA is vinyl acetate.
4. heat curing-type compound thermal shrink sleeve according to claim 1, is characterized in that: the composition of described 15 parts of auxiliary agents concrete proportioning is by volume that carbon black is 3 parts; Fire retardant is 5 parts, aluminium hydroxide; Sensitizer is 2 parts; Lubricant is 2 parts; Antioxidant is 3 parts.
5. according to the heat curing-type compound thermal shrink sleeve described in any one in claims 1 to 3, it is characterized in that: the component of described reaction type hot-fusible glue-line (10) by volume proportioning is: 50～70 parts of polyolefin elastomers, 5～10 parts of flexibilizer, 22～30 parts of tackifying resins, 1～5 part, antioxidant, 1～3 part of polymerization inhibitor, 1～2 part of thermal initiator.
6. a manufacture method for heat curing-type compound thermal shrink sleeve described in any one in claim 1 to 5, is characterized in that: the method comprises the following steps: A. by the internal layer of reaction type hot-fusible glue and outer field major ingredient for the polyolefinic coextrusion mold of thermoplastics type be composite bushing; B. by high-energy electron accelerator, this sleeve pipe is carried out to irradiation, control is only crosslinked for cladding material, and inner layer material is crosslinked; C. by heating, internal diameter is expanded.
7. the manufacture method of heat curing-type compound thermal shrink sleeve described in any one in a claim 1 to 5, it is characterized in that: the method comprises the following steps: A '. reaction type hot-fusible glue internal layer is coated in to major ingredient on the outer field inwall of thermoplastics type's polyolefin, forms composite bushing; B '. by high-energy electron accelerator, this inner layer material and cladding material are carried out to irradiation, control is only crosslinked for cladding material, and inner layer material is crosslinked; C '. by heating, internal diameter is expanded.
8. manufacture method according to claim 7, is characterized in that: the thickness of internal layer described in steps A is 0.5～1.5mm, and extrusion temperature is 70～130 ℃; Outer layer thickness is 1～5mm, and extrusion temperature is 90～150 ℃; The parameter of high-energy electron accelerator described in step B is 3.0Mev, 30mA, and irradiation dose is 4～12Mrad, and irradiation speed is 1～150m/min according to ectonexine thickness sum and product diameter adjusting range; In step C, adopt heating pressurization expanded inner diameter, heating-up temperature is 120～150 ℃, and pressure control is 0.1MPa～0.7MPa, and 2～5 times for original diameter are controlled in internal diameter expansion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210239715.3A CN102709007B (en) | 2012-07-12 | 2012-07-12 | Thermal setted coextruded heat shrinkable sleeving and method for producing same |
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| CN201210239715.3A CN102709007B (en) | 2012-07-12 | 2012-07-12 | Thermal setted coextruded heat shrinkable sleeving and method for producing same |
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| CN102709007B true CN102709007B (en) | 2014-07-02 |
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| US10566757B2 (en) * | 2016-12-09 | 2020-02-18 | Lear Corporation | Method of heat shrinking a protective sleeve onto an electrical connection |
| CN106932859A (en) * | 2017-04-17 | 2017-07-07 | 南京邮电大学 | A kind of method for improving Optical Fiber Transmission power threshold |
| JP6965595B2 (en) * | 2017-06-23 | 2021-11-10 | 住友電気工業株式会社 | Electric wire with terminal and its manufacturing method |
| JP7286993B2 (en) * | 2019-02-14 | 2023-06-06 | 住友電装株式会社 | Ground terminal and wire harness |
| JP6743927B1 (en) * | 2019-02-14 | 2020-08-19 | 住友電装株式会社 | Ground terminal and wire harness |
| CN111393733A (en) * | 2020-04-03 | 2020-07-10 | 江苏鼎尚电子材料股份有限公司 | Environment-friendly flame-retardant heat-shrinkable tubing and preparation method thereof |
| CN114156025A (en) * | 2021-11-13 | 2022-03-08 | 广西电网有限责任公司南宁供电局 | Insulating sleeve |
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| US5914160A (en) * | 1994-11-04 | 1999-06-22 | Sumitomo Electric Industries, Ltd. | Adhesive tube composite tube and method for sealing using the same |
| CN1327908A (en) * | 2001-07-05 | 2001-12-26 | 卢沛女 | Method for manufacturing thermally shrinking dual-layer sleeved tube |
| CN101987892A (en) * | 2009-07-31 | 2011-03-23 | 上海长园电子材料有限公司 | Heat-shrinkable tubing and material thereof |
| CN102153966A (en) * | 2011-02-24 | 2011-08-17 | 中科英华湖州工程技术研究中心有限公司 | Special hot melt adhesive for mating 1E-grade K1-type cable accessories for nuclear power station |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08216314A (en) * | 1995-02-08 | 1996-08-27 | Kobunshi Giken Kk | Heat-shrinkable double-layer tube and sheet for covering metal, and method for covering metal with them |
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2012
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| US5914160A (en) * | 1994-11-04 | 1999-06-22 | Sumitomo Electric Industries, Ltd. | Adhesive tube composite tube and method for sealing using the same |
| CN1327908A (en) * | 2001-07-05 | 2001-12-26 | 卢沛女 | Method for manufacturing thermally shrinking dual-layer sleeved tube |
| CN101987892A (en) * | 2009-07-31 | 2011-03-23 | 上海长园电子材料有限公司 | Heat-shrinkable tubing and material thereof |
| CN102153966A (en) * | 2011-02-24 | 2011-08-17 | 中科英华湖州工程技术研究中心有限公司 | Special hot melt adhesive for mating 1E-grade K1-type cable accessories for nuclear power station |
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Address after: 518000 Guangdong city of Shenzhen province Pingshan New District Office Kengzi sands community Joint Industrial Zone No. 1 building Patentee after: Shenzhen Bonseal New Material Co., Ltd. Address before: 518000, Shenzhen, Guangdong province Baoan District Mission Street Si Si Road south section of hung United Eagle Technology Park Patentee before: Shenzhen Bonseal New Material Co., Ltd. |