• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention comprises a transfer element (2), a ignition element (3) and a flame retardant coating film (4) surrounding the ignition element (3), wherein the acrylate, methacrylate, epoxy, vinyl ether, allyl ether and oxetane A flame retardant cable (1) made of a material based on a polymer obtained from a polymeric liquid composition comprising at least one polymer precursor with a selected functional group, said material comprising at least one phosphorus group.
    公开号:KR20040047697A
    申请号:KR1020030085044
    申请日:2003-11-27
    公开日:2004-06-05
    发明作者:올리비에 뼁또
    申请人:넥쌍；
    IPC主号:
    专利说明:

    Flame retardant cable
    [2] The present invention relates to a flame-retardant cable.
    [3] In a known manner, electrical and / or optical cable acquirers for power transport and / or information transmission attempt to avoid spreading smoke through the cable even if the cable is laid vertically in a fire, and the insulation material covering the cable core melts off at high temperatures. To prevent it.
    [4] European patent application EP'1'191'547'A1 discloses a cable which is preferably coated with a thin outer film of 5 to 50 μm thickness and which has a polyethylene insulation film which serves for example to protect against spreading fires. The coating is formed by ultraviolet irradiation of a polyacrylate polymer.
    [5] Not all polyacrylate coatings can provide a cable that can delay the deterioration of the cable and preserve its operability even when exposed to flames or sparks.
    [6] Moreover, it is important that the outer coating has good antiwear properties.
    [7] It is an object of the present invention to devise a flame retardant cable which is preferably inexpensive, easy to manufacture and fast.
    [8] Another object of the present invention is to devise an anti-wear cable.
    [9] To this end, the present invention provides a polymer obtained from a polymeric liquid composition containing at least one polymer precursor comprising a transfer element, a ignition element and a functional group selected from acrylate, methacrylate, epoxy, vinyl ether, allyl ether and oxetane. It provides a flame retardant cable prepared from a material based on the flame retardant coating surrounding the printing element, wherein the material contains at least one phosphorus group.
    [10] The phosphorus group (s) provide the flame-retardant property of the coating of the present invention.
    [1] 1 is a cross-sectional view of a power cable of the present invention.
    [11] In a preferred embodiment, the phosphorus group may be chemically bonded to the polymer, in which embodiment the precursor of the polymer may comprise at least one phosphorus group.
    [12] Preferably, the material of the present invention may be free of halogen, which is an element conventionally used as a flame retardant.
    [13] According to a feature of the invention, the combustible element may be selected from at least one of an insulating film, a sheath, a reinforcing element, an optical fiber protective tube, a corrugated core, a substring, a tape and a braid.
    [14] If the combustible element is an insulating film, the insulating film may be a material made from a halogen-free thermoplastic polymer, preferably polyethylene having good dielectric properties.
    [15] For example, in the field of telecommunication cables, often vertically installed in ventilators, the polyethylene protected by the flame retardant coating of the present invention is polytetrafluoroethylene (PTFE) or tetrafluoroethylene and hexafluorine which is more resistant to flame but less dielectric. Low propylene copolymers (fluorinated ethylene propylene copolymers, FEP) can be advantageously replaced.
    [16] The combustible device may contain its own flame retardant mineral filler but insufficient protection against flame. In this form, the flame retardant coating enhances the fire resistance of the device.
    [17] In an aspect of the invention, the transmission element is selected from photoconductors and conductors.
    [18] In a first aspect, the flame retardant coating film is prepared by applying the polymeric liquid composition to the combustible device using a coating technique selected from applications using sprays, dipping, impregnation, and brushes.
    [19] In a second aspect, the flame retardant coating film is formed from a tape injected into the polymeric liquid composition and wound on the combustible element.
    [20] Advantageously, the polymeric liquid composition may comprise a reactive diluent comprising an anti-wearable compound, preferably having an annular structure, and at least one functional group that selectively reacts with one of the functional groups of the polymer precursor. Include.
    [21] As such, the coating not only has high flame retardancy, but also withstands wear and exhibits good thermodynamic properties. In addition, anti-wear compounds are easy to miscible and make the composition easy to apply.
    [22] The composition can be polymerized by, for example, actinic radiation (ultraviolet radiation, electrons, gamma rays, etc.).
    [23] Polymeric precursors (monomers, oligomers) comprising an acrylate functional group and at least one phosphorus group are sold by UCB Chemical, for example, as ebecryl IRR 527.
    [24] The weight part value of the anti-wearable compound relative to 100 parts by weight of the composition is preferably less than 95 and preferably lies in the range of 10 to 30 to preserve the high fire resistance properties of the coating.
    [25] When the anti-wearable compound comprises at least one acrylate functional group, the acrylate equivalent of the anti-wearable compound is preferably greater than 80 and preferably substantially the same as 210.
    [26] The term "acrylate equivalent weight" means the molecular weight of a compound relative to the number of acrylate functional groups in one molecule.
    [27] Thus, the coating film exhibits good mechanical properties, in particular good elasticity (high burst elongation) and increased hardness.
    [28] The liquid composition is preferably polymerized by actinic radiation, wherein when the actinic radiation is of ultraviolet type, the composition may comprise a photoinitiator and the number of parts by weight of this photoinitiator relative to 100 parts by weight of the composition ranges from 0.1 to 10. And, preferably, the number is substantially equal to three.
    [29] The liquid composition is advantageously polymerized by ultraviolet irradiation and comprises:
    [30] 80 parts by weight of the polymer precursor polymerized by ultraviolet light and halogen-free oligomer;
    [31] 17 parts by weight of isobornyl acrylate; And
    [32] 3 parts by weight of photoinitiator
    [33] Other features and advantages of the invention emerge from the example descriptions set forth in the following non-limiting examples.
    [34] Examples 1 and 2 relate to a liquid composition which is polymerized by actinic radiation type irradiation to provide a flame retardant coating film of a power cable, a data cable or a communication cable.
    [35] Example 1
    [36] Composition 1
    [37] 97 parts by weight of evercryl IRR 527 from UCB Chemical, a halogen-free polyester acrylate oligomer having two acrylate functional groups and a phosphorus group; And
    [38] CIBA photoinitiator DAROCUR1173 (chemical name) 3 parts by weight.
    [39] Example 2
    [40] Composition 2
    [41] 80 parts by weight of evercryl IRR # 527;
    [42] 17 parts by weight of isobornyl acrylate of cyclic structure, such as Genomer 1121 from RAHN, having an equivalent weight of acrylate equal to 208; And
    [43] 3 parts by weight of photoinitiator DAROCUR1173 (chemical name).
    [44] Table 1 provides the properties of Coating 1 made of a polymer based material obtained by polymerizing Composition 1 by UV irradiation and the properties of Coating 2 made of a polymer based material obtained by polymerizing Composition 2 by UV irradiation. do.
    [45] In this embodiment, the precursor also includes a phosphorus group and the resulting polymer is chemically bonded to the phosphorus group.
    [46] Coating 1Coating 2 Burst Strength (MPa) at 25 ℃13.421.4 Rupture Elongation (%)4643.1 Strength (Buchholz Method)<59123
    [47] Composition 1, when heated to 60 ° C., exhibits a viscosity equivalent to about 17,000 millipascal-seconds (mPa · s). Composition 2 has a viscosity of about 1206 mPa · s at 50 ° C., resulting in coating 2 which is easier to apply than composition 1 and exhibits good stretch and better antiwear properties.
    [48] The use of isobornyl acrylate improves the mechanical properties and anti-wear properties of the coating. In addition, this compound having an acrylate functional group that reacts with one of the acrylate functional groups of the oligomers can achieve full polymerization using a medium pressure mercury vapor lamp that emits in the ultraviolet and mainly at wavelengths from 200 nm to 400 nm. Such lamps are then sold, for example by fusion carrying 200 W / cm power, the cable is delivered at a speed of 80 m / min and exposed in a single path even when the coating thickness is 100 μm.
    [49] As a variant, one or the other of Compositions 1 and 2 may comprise pigments, fillers, diffusion aids or sliding aids, adhesion promoters, ultraviolet stabilizers and antioxidants.
    [50] Table 2 below provides the test results performed by applying the ISO 4589-2 protocol to measure the oxygen limit index (OLI), self-extinguish time and combustion length of five samples to characterize their flame retardancy.
    [51] Comparative Sample 1 includes a power cable outer membrane material composed of ethylene vinyl acetate (EVA) copolymer comprising a flame retardant mineral filler such as aluminum trihydrate, Al 2 O 3 , 3H 2 O.
    [52] Each of Samples 2 and 3 comprises a fill membrane covered in an outer membrane flame retardant cover of ethylene vinyl acetate (EVA) similar to Sample 1 but of a polymer based material obtained from Composition 1 of the present invention.
    [53] Samples 4 and 5 each included a filled ethylene vinyl acetate (EVA) membrane similar to Sample 1 and covered with an outer membrane flame retardant coating based on a polymer obtained from Composition 2 of the present invention.
    [54] Due to the outer membrane of the present invention, samples 2, 3 and 5 show OLI 5% larger (only 1% larger than sample 4) than in sample 1.
    [55] The outer membrane of the invention in Sample 4 exhibits an OLI greater than 1% than in Sample 1.
    [56] Sample numberOuter film thickness (㎛)OLI (%)Digestion time (s)Combustion length (mm) One-32> 12010 2403717535 3703717035 45033585 51003710310
    [57] When using isobornyl acrylate, the coating thickness needs to be increased to obtain OLI of 37%. Nevertheless, from the tests performed on Sample 5, it was observed that this compound can increase the mechanical properties and anti-wear properties of the coating, as well as reduce its burn time and shorten the digestion time.
    [58] Table 3 below provides test results for three vertical cables, which were performed using the IEC 3321 protocol. This test is applied for 60 seconds with a cable or insulator conductor in a vertical position, filled with a mixture of air and propane at a flow rate of 4 l / min and 640 ml / min, respectively, at a 45 ° angle to the vertical axis of the sample. It consists of placing the flame from the burner and then measuring the extinguishing and burning times.
    [59] Cable 1 comprises a copper conductor having a section of 16 square millimeters (mm 2 ) coated with a flammable insulating film made of a compound comprising polyethylene crosslinked by a silane process and no other flame retardant mineral filler.
    [60] Both cable 2 and cable 3 comprise similar copper conductors as in cable 1, each of which is coated with an insulating film similar to that in cable 1, which is then obtained from composition 1 in one case and in another case. It is coated with a flame-retardant coating envelope made from a polymer based material obtained from 2.
    [61] Polymerization is performed by a 200 mW / cm UV lamp and the cable is delivered at a rate of 50 mW / min.
    [62] Cable numberOuter film coating thickness (㎛)Digestion timeCombustion length (mm) One-> 4 '440 2412'28 "135 31002'26 "95
    [63] The cable shall pass the test when the length of the combustion above the flamed zone does not exceed 425 mm. As expected, Cable 1 did not pass the test. In addition, the combustion length of cable 3 is shorter than that of cable 2.
    [64] 1 is a cross-sectional view of a power cable of the present invention.
    [65] For example, the cable 1 comprises a transmission element 2, for example, a conductor made of copper, a flammable insulating film 3 coating the transmission element, and a flame retardant coating film 4 coating the insulating film 3 itself, and the flame retardant coating film 4 is, for example, It is made of a polymer based material obtained from composition 2 and the thickness is preferably about 100 μm.
    [66] Coating film 4 of the present invention is an outer film existing on the insulating film, which imparts flame retardancy and preferably imparts anti-wear properties. Nevertheless, cable 1 may naturally comprise one or more other films between the insulating film and the film 4 of the present invention.
    [67] A flame retardant coating film is made by applying a polymeric liquid composition to a flammable insulating film using a conventional coating technique such as a brush method or a spray method.
    [68] In one variation, the flame retardant coating film is made from a tape injected into the composition and wound around an insulating film.
    [69] The invention is equally applicable to all flammable elements used in communication cables or power cables, such as reinforcing elements, optical fiber protection tubes, padding elements, groove corecore braids.
    [70] More generally, the present invention can be used equally for power cables and communication cables and also for fiber optic cables.
    权利要求:
    Claims (15)
    [1" claim-type="Currently amended] A flame retardant cable (1) comprising a transmission element (2), a flammable element (3) and a flame retardant coating film (4) surrounding the flammable element (3), comprising acrylates, methacrylates, epoxies, vinyl ethers, allyl ethers and In the flame retardant cable (1) made of a polymer based material obtained from a polymeric liquid composition comprising at least one polymer precursor comprising a functional group selected from oxetane,
    Flame retardant cable (1), characterized in that the material comprises at least one phosphorus group.
    [2" claim-type="Currently amended] 2. Flame retardant cable (1) according to claim 1, characterized in that the phosphorus group is chemically bonded to the polymer.
    [3" claim-type="Currently amended] 3. Flame retardant cable (1) according to claim 1 or 2, characterized in that the polymer precursor comprises at least one phosphorus group.
    [4" claim-type="Currently amended] Flame retardant cable (1) according to any one of the preceding claims, characterized in that the material is halogen free.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4, wherein the flammable element is selected from one or more of an insulating film, an outer film, a reinforcing element, an optical fiber protection, a padding element, a groove core, a tape, and a braid. , Flame retardant cable (1).
    [6" claim-type="Currently amended] Flame retardant cable (1) according to any one of the preceding claims, characterized in that when the flammable element is an insulating film, the insulating film is made of a material selected from a halogen-free thermoplastic polymer, preferably polyethylene.
    [7" claim-type="Currently amended] 7. Flame retardant cable (1) according to any one of the preceding claims, characterized in that the transmission element is selected from optical and electrical conductors.
    [8" claim-type="Currently amended] 8. The flame retardant coating according to claim 1, wherein the flame-retardant coating is made by applying the polymeric liquid composition to the flammable device using a coating technique selected from spraying, dipping, impregnation and brushing applications. Characterized in that, the flame-retardant cable (1).
    [9" claim-type="Currently amended] The flame retardant cable (1) according to any one of the preceding claims, wherein the flame retardant coating film is made from a tape injected into the polymeric liquid composition and wound around the flammable element.
    [10" claim-type="Currently amended] 10. The at least one of claim 1, wherein the polymeric liquid composition comprises an anti-wear compound, preferably of a cyclic structure, and optionally reacts with one of the functional groups of the polymer precursor. Flame retardant cable (1), characterized in that it comprises a reactive diluent comprising a functional group of.
    [11" claim-type="Currently amended] Flame retardant cable (1) according to claim 10, characterized in that the parts by weight value of the anti-wear compound relative to 100 parts by weight of the liquid composition is less than 95, preferably in the range of 10 to 30.
    [12" claim-type="Currently amended] 12. The acrylate equivalent weight of claim 10 or 11 wherein the anti-wear compound comprises at least one acrylate functional group, wherein the acrylate equivalent weight of the anti-wear compound is greater than 80, preferably substantially equal to 210. Characterized in that, the flame-retardant cable (1).
    [13" claim-type="Currently amended] The flame retardant according to any one of claims 1 to 12, wherein the liquid composition is polymerized by actinic radiation and the composition comprises a photoinitiator when the actinic radiation is UV type. Cable (1).
    [14" claim-type="Currently amended] Flame retardant cable (1) according to claim 13, characterized in that the weight part value of the photoinitiator to 100 parts by weight of the composition is substantially equal to 0.1 to 10, preferably 3.
    [15" claim-type="Currently amended] The liquid composition according to any one of claims 1 to 14, wherein the liquid composition is polymerized by UV irradiation, 80 parts by weight of the polymer precursor which is a halogen-free oligomer, 17 parts by weight of isobornyl acrylate, and 3 parts by weight of photoinitiator. It characterized in that it comprises a flame retardant cable (1).
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    同族专利:
    公开号 | 公开日
    FR2848016B1|2005-01-28|
    KR20110033828A|2011-03-31|
    EP1424703A1|2004-06-02|
    FR2848016A1|2004-06-04|
    KR101132735B1|2012-04-06|
    US20110110632A1|2011-05-12|
    US20040151906A1|2004-08-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-11-29|Priority to FR0215065A
    2002-11-29|Priority to FR0215065
    2003-11-27|Application filed by 넥쌍
    2004-06-05|Publication of KR20040047697A
    优先权:
    申请号 | 申请日 | 专利标题
    FR0215065A|FR2848016B1|2002-11-29|2002-11-29|Flame retardant|
    FR0215065|2002-11-29|
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