CN101759904B - Middle and low-pressure halogen-free flame retarding single-wall heat-shrinkable tube and manufacturing method thereof - Google Patents
Middle and low-pressure halogen-free flame retarding single-wall heat-shrinkable tube and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract description 4
- 230000000979 retarding effect Effects 0.000 title 1
- 239000003063 flame retardant Substances 0.000 claims abstract description 78
- 229920000098 polyolefin Polymers 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims description 125
- 239000000203 mixture Substances 0.000 claims description 108
- 239000007822 coupling agent Substances 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 53
- 230000008878 coupling Effects 0.000 claims description 36
- 238000010168 coupling process Methods 0.000 claims description 36
- 238000005859 coupling reaction Methods 0.000 claims description 36
- 239000007921 spray Substances 0.000 claims description 36
- 239000005995 Aluminium silicate Substances 0.000 claims description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 26
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 24
- 239000000347 magnesium hydroxide Substances 0.000 claims description 24
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 24
- -1 polydimethylsiloxane Polymers 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003381 stabilizer Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 206010070834 Sensitisation Diseases 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 230000008313 sensitization Effects 0.000 claims description 15
- 239000012188 paraffin wax Substances 0.000 claims description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000779 smoke Substances 0.000 claims description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- 239000006084 composite stabilizer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 2
- FJRUWRJAJNEIKD-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-6,7-diamine Chemical compound O1CCOC2=C1C=C(N)C(N)=C2 FJRUWRJAJNEIKD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a heat-shrinkable tube, in particular to a middle and low-pressure halogen-free flame-retarding single-wall heat-shrinkable tube and a manufacturing method thereof. The tube is composed of a wall. The material of the comprises the following components by mass: 70 portions of polyolefine mixed resin, 10 portions of auxiliary agent, 20 portions of flame retardant and 10 portions of auxiliary flame retardant. The manufacturing method comprises the step of preparing the inner wall material of the single-wall heat-shrinkable tube, extruding, radiating, expanding and forming. Compared with the traditional technology for manufacturing heat-shrinkable tube, the invention has the characteristics that the halogen-free flame retardant is adopted, the product has good flame retardant effectiveness, high temperature resistance, no pollution even in combustion and low cost; the product is applicable to operating under the conditions of 10 kV, has significant economical benefits and environment protection benefits, and is suitable for large-scale popularization and application.
Description
One, technical field:
The present invention relates to a kind of heat-shrinkable tube, be specifically related to a kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube and preparation method thereof.
Two, background technology
The thermal contraction single-walled pipe of Xiao Shouing in the market, can be widely used in Aeronautics and Astronautics, boats and ships, automobile, household electrical appliances, communication, field of petrochemical industry, electric wire junction and bifurcation be played the effect such as anticorrosion, against shock dislocation of fire-retardant, sealed damp-proof, waterproof, circuit.What use in the prescription of layered material outside routine is halogen-containing fire retardant, the time has the height highly toxic drawback of being fuming in burning, causes the secondary disaster of fire easily.Current country is more and more higher to requirement on environmental protection, has adopted not halogen-containing fire retardant in a lot of fields, and the environmental protection organization of EU member country has also delivered the decree that the plastics of forbidding halogen-containing flame retardant enter the European market.But there is shortcoming of low quality, that cost is high or flame retardant effect is bad in the twin wall emitter lateral for halogen-free flame-retardant in the prior art more.
Three, summary of the invention:
Technical purpose
The purpose of this invention is to provide a kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube and preparation method thereof; adopt halogen-free flame retardants in the raw material; the good flame retardation effect of product; high temperature resistant, have a good performance; even it is also pollution-free during burning; cost reduces, and has remarkable economic efficiency and environmental protection benefit, is fit to apply on a large scale.
Technical scheme
The present invention has following technical scheme to finish: a kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent;
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make;
Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is characterized in that:
A. the preparation of wall material:
Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make by mass percentage; Auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned raw material adding Banbury mixer or height are stirred machine, stirring the back adds in the twin-screw mixer machine, under 140～160 ℃ temperature condition, through fully stirring and banburying, screw speed 125rpm, 110～135 ℃ of melting temperatures fully merge each component, be prepared into the wall material of described mesolow halogen-free fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. extrude:
The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C. irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D. expansion:
The mesolow halogen-free fire retardant single-wall heat-shrinkable tube that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the single-walled pipe work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described mesolow halogen-free fire retardant single-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
The main production equipments inventory
| Machinery or device name | Model specification | The country origin place of production | Rated output |
| Rumbatron | DD | Chinese Shanghai | 2.0Mev |
| Multi-functional irradiation transmission system | / | Chinese Shanghai | 80KW |
| The granulation Banbury mixer | 75L | Chinese Shanghai | 150KW |
| Forcing machine | SJ-120 | The China Zhangjiagang | 123KW |
| Twin screw extruder | TE-70 | Nanjing of China | 75KW |
Principle: because cross-linking radiation changes polyolefinic molecular structure, this variation makes polyolefine have memory effect under certain condition.Heat-shrinkable tube utilizes the principle of this memory effect just, behind the heat-shrinkable tube work in-process cross-linking radiation, with behind its expansion cooling and shaping, is exactly finished product after the heating.In use, the heating back is because memory effect retracts to the preceding state of expansion again.
Beneficial effect:
1, adopt special halogen-free flame retardants in the raw material, the good flame retardation effect of product, high temperature resistant, have good performance, even also pollution-free during burning, cost reduces, and has remarkable economic efficiency and environmental protection benefit, is fit to apply on a large scale.
2, being suitable for the 10kV high pressure conditions uses down.
3, the technical characterstic internal layer thermosol of the more traditional collapsible tube of this product can waterproof sealing, and outer layered material has kept characteristics such as ordinary hot draw good electrical properties and chemical property, so Application Areas is more extensive.
4, remedied the shortcoming that the ordinary hot collapsible tube can not waterproof sealing.This product possesses whole use propertieies of ordinary hot collapsible tube fully, has also possessed performances such as waterproof sealing moisture-proof anticorrosive simultaneously.
5, this product satisfies the environmental requirement of state ROHS such as European Union instruction fully, has that low temperature shrinks, three times to four times stable expansions, has advantages such as vertical shrinking percentage is low.
Four, embodiment
Embodiment 1
A kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make;
Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily.
Rosin 1-5 part in described second auxiliary agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB.
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of mesolow halogen-free fire retardant single-wall heat-shrinkable tube,
A. the preparation of wall material:
Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make by mass percentage; Auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned raw material adding Banbury mixer or height are stirred machine, stirring the back adds in the twin-screw mixer machine, under 140～160 ℃ temperature condition, through fully stirring and banburying, screw speed 125rpm, 110～135 ℃ of melting temperatures fully merge each component, be prepared into the wall material of described mesolow halogen-free fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. extrude:
The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C. irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D. expansion:
The mesolow halogen-free fire retardant single-wall heat-shrinkable tube that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the single-walled pipe work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described mesolow halogen-free fire retardant single-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Embodiment 2
A kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent; The olefin resin is the polyolefine hybrid resin that 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA2200 make;
Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is characterized in that:
A. the preparation of wall material:
Described wall material is that 10 parts and ignition dope are formed for 37 parts by 53 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin that the polyolefine hybrid resin makes for 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220 by mass percentage; Auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned raw material adding Banbury mixer or height are stirred machine, stirring the back adds in the twin-screw mixer machine, under 140～160 ℃ temperature condition, through fully stirring and banburying, screw speed 125rpm, 110～135 ℃ of melting temperatures fully merge each component, be prepared into the wall material of described mesolow halogen-free fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. extrude:
The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C. irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D. expansion:
The mesolow halogen-free fire retardant single-wall heat-shrinkable tube that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the single-walled pipe work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described mesolow halogen-free fire retardant single-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Embodiment 3
A kind of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent;
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220 make;
Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of mesolow halogen-free fire retardant single-wall heat-shrinkable tube is characterized in that:
A. the preparation of wall material:
Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 70 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin that the polyolefine hybrid resin makes for 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220 by mass percentage; Auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned raw material adding Banbury mixer or height are stirred machine, stirring the back adds in the twin-screw mixer machine, under 140～160 ℃ temperature condition, through fully stirring and banburying, screw speed 125rpm, 110～135 ℃ of melting temperatures fully merge each component, be prepared into the wall material of described mesolow halogen-free fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. extrude:
The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C. irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D. expansion:
The mesolow halogen-free fire retardant single-wall heat-shrinkable tube that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the single-walled pipe work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described mesolow halogen-free fire retardant single-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Claims (3)
1. mesolow halogen-free fire retardant single-wall heat-shrinkable tube, it is characterized in that: be made up of the wall material, according to mass fraction, described wall material is made up of for 10 parts 70 parts of polyolefine hybrid resins, 10 parts of auxiliary agents, 20 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is magnesium hydroxide or aluminium hydroxide;
Described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make by mass percentage; Described auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin;
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method just to account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder grain weight amount 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant;
Described coupling agent A is a silane coupling agent 550, and coupling agent B is the line style polydimethylsiloxane, and coupling agent C is an octadecanoic acid, and coupling agent D is a tetra-sodium type monoalkoxy class titanic acid ester.
2. mesolow halogen-free fire retardant single-wall heat-shrinkable tube according to claim 1 is characterized in that: described antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester; Anti copper agent is a hydroxy-terminated polybutadienes vinyl cyanide fluid rubber; Processing stabilizers is that rare-earth stabilizer REC-LS-D or REC-LS-F smoke suppressor are zinc borate; The sensitization crosslinking coagent is a TriMethylolPropane(TMP).
3. mesolow halogen-free fire retardant single-wall heat-shrinkable tube according to claim 1 and 2 is characterized in that: described polyolefine hybrid resin is the polyolefine hybrid resin that makes of 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220 by mass percentage; Described auxiliary agent is that antioxidant is 1 part, 1 part of anti copper agent, and 2 parts of processing stabilizers, 3 parts of smoke suppressors, 1 part of sensitization crosslinking coagent, surplus is a paraffin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101850430A CN101759904B (en) | 2009-10-28 | 2009-10-28 | Middle and low-pressure halogen-free flame retarding single-wall heat-shrinkable tube and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101850430A CN101759904B (en) | 2009-10-28 | 2009-10-28 | Middle and low-pressure halogen-free flame retarding single-wall heat-shrinkable tube and manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101759904A CN101759904A (en) | 2010-06-30 |
| CN101759904B true CN101759904B (en) | 2011-09-28 |
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| CN2009101850430A Expired - Fee Related CN101759904B (en) | 2009-10-28 | 2009-10-28 | Middle and low-pressure halogen-free flame retarding single-wall heat-shrinkable tube and manufacturing method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN101759904B (en) |
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Effective date of registration: 20201015 Address after: Wujiang District of Suzhou city in Jiangsu province 215200 Li Zhen Bei she Community Road No. 1288. Patentee after: Jiangsu Dasheng Thermal Shrinkage Protection Products Co.,Ltd. Address before: 215214 Wujiang City, Jiangsu province FenHu Beishe Community Road No. 1288. Patentee before: JIANGSU DASHENG PYROCONDENSATION MATERIAL Co.,Ltd. |
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